TWI542627B - A crumb of the block copolymer and a binder composition - Google Patents

Description

Block copolymer crumb and adhesive composition

The present invention relates to a crumb of a block copolymer and an adhesive composition using the same.

In recent years, in view of energy saving, resource saving, and environmental load reduction, hot-melt adhesives have been widely used, and as a base polymer of hot-melt adhesives, vinyl aromatic monomers have been widely used. A conjugated diene single-system block copolymer (for example, SBS: styrene-butadiene-styrene-block copolymer, etc.). However, the adhesive composition obtained by using these block copolymers has insufficient balance of holding power, viscosity, and adhesion, and such improvement is desired, and many proposals have been made.

For example, Patent Document 1 discloses an adhesive composition comprising a triblock copolymer and a diblock copolymer. Patent Document 2 discloses an adhesive composition comprising a block copolymer obtained by coupling with a specific bifunctional coupling agent (specific dihalogen compound). Patent Document 3 discloses an adhesive composition comprising a block copolymer obtained by hydrogenating a block copolymer of a vinyl aromatic monomer and a conjugated diene monomer at a specific ratio.

These polymers are generally sold in the form of granules because they are easier to handle. Patent Document 4 discloses a block copolymer which controls the form of the fracture under specific conditions.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. Hei 61-278578

[Patent Document 2] Japanese Patent Laid-Open Publication No. SHO 63-248817

[Patent Document 3] Japanese Patent Laid-Open No. Hei 05-98130

[Patent Document 4] International Publication WO2012/056939

However, even in the above-mentioned prior art, there are problems in the solubility of the block copolymer, the transportability, the melt viscosity of the adhesive composition, and the odor, and further, the balance of these characteristics is also insufficient.

The present invention has been made in view of the problems of the prior art described above, and an object thereof is to provide an excellent dispersibility, a dissolving property, a low odor characteristic, and a low odor characteristic, if used in an adhesive composition. A crushed product of a block copolymer of an adhesive composition excellent in balance of these characteristics, and an adhesive composition containing the crushed product of the block copolymer.

The inventors of the present invention have intensively studied in order to solve the problems of the prior art described above, and as a result, found that the fractured product of the block copolymer of a specific structure and the crushed material and the adhesion-imparting agent are respectively adhered in a specific amount. The composition of the present invention solves the problems of the prior art described above, thereby completing the present invention.

That is, the present invention is as follows.

A crushed product of a block copolymer comprising at least one polymer block mainly composed of a vinyl aromatic hydrocarbon monomer unit, and at least one polymerized with a conjugated diene compound monomer unit as a main component block was a necessary condition, and a weight average molecular weight of 20,000 to 1,000,000, and satisfies the following (a) ~ (c) of: (a) a specific surface area of 0.000001m ² / g or more and less than 0.3m ² / g (b) The cumulative pore volume of the pores having a pore radius of 1 μm to 100 μm is 0.05 mL/g or more and less than 1.0 mL/g, and (c) the average pore radius is 0.00001 μm or more and 1.5 μm or less.

2 according to the aspect of the block copolymer 1 was crushed, wherein said specific surface area of 0.000001m ² / g or more and 0.2m ² / g or less.

3. The crushed product of the block copolymer according to the above 1 or 2, wherein the average pore radius is 1.0 μm or less.

4. The crushed product of the block copolymer according to any one of the above 1 to 3, wherein the maximum value of the log differential pore indentation volume when the pore radius is 1 μm or more and 100 μm or less is divided by the pore radius 0.001 μm. The value obtained by the maximum value of the log differential pore indentation volume when the above is less than 1 μm ((the maximum value of the log differential pore indentation volume when the pore radius is 1 μm to 100 μm) / (the pore radius is 0.001 μm or more) The maximum value of the log differential pore indentation volume when the particle size is less than 1 μm is 0.1 to 2.

5. The crushed product of the block copolymer according to any one of the above 1 to 4, which has a cumulative pore volume of 0.0001 mL/g or more and less than 0.6 mL/g.

6. The crushed product of the block copolymer according to any one of the above 1 to 5, which has a cumulative pore volume of 0.0001 mL/g or more and less than 0.4 mL/g.

7. The crushed product of the block copolymer according to any one of the above 1 to 6, wherein the pore volume of the pores having a pore radius of from 1 μm to 100 μm is 0.08 mL/g or more.

8. The crushed product of the block copolymer according to any one of the above 1 to 7, wherein the cumulative pore volume of the pores having a pore radius of 1 to 100 μm is divided by the pore radius of 0.001 μm or more and 100 μm or less. The value obtained by accumulating the pore volume of the pores (the cumulative pore volume of the pores having a pore radius of 1 μm to 100 μm) / (the cumulative pore volume of the pores having a pore radius of 0.001 μm to 100 μm) It is 0.30 or more and 0.80 or less.

9. The crushed product of the block copolymer according to any one of the above 1 to 8, wherein the cumulative pore volume of the pores having a pore radius of from 1 to 100 μm is divided by the pore radius of 0.001 μm. The value obtained by accumulating the pore volume of the above pores of 100 μm (the cumulative pore volume of the pores having a pore radius of from 1 μm to 100 μm) / (the cumulative pores of the pores having a pore radius of from 0.001 μm to 100 μm) The volume)) is 0.40 or more and 0.77 or less.

The crushed product of the block copolymer according to any one of the above 1 to 9, wherein the content of the vinyl aromatic monomer unit in the block copolymer is 5% by mass or more and less than 20% by mass.

The crushed product of the block copolymer according to any one of the above 1 to 10, wherein the content of the vinyl aromatic hydrocarbon unit in the block copolymer is 20% by mass or more and 50% by mass or less.

The crushed product of the block copolymer according to any one of claims 1 to 11, wherein the block copolymer is a block copolymer composition comprising the component (A) and the component (B), and the above components (A) a polymer block containing at least one polymer block mainly composed of a vinyl aromatic hydrocarbon and at least one polymer block mainly composed of a conjugated diene compound, and having a weight average molecular weight of 20,000 or more and 500,000 or less The component (B) contains at least one polymer block mainly composed of a vinyl aromatic hydrocarbon and at least one polymer block mainly composed of a conjugated diene compound, and has a weight average molecular weight of 30,000 or more. The ratio of the weight average molecular weight of the component (A) to the component (B) (weight average molecular weight of the component (B)) / (weight average molecular weight of the component (A)) is from 1 to 10,000,000.

The crushed product of the block copolymer according to the above 12, wherein the component (A) is 20% by weight or more and 90% by weight or less, and the component (B) is 10% by weight or more and 80% by weight or less.

14. The crushed product of the block copolymer according to the above 12 or 13, wherein the component (A) has a weight average molecular weight of less than 200,000.

15. The crushed product of the block copolymer according to the above 12 or 13, wherein the component (A) has a weight average molecular weight of 70,000 or more and 500,000 or less.

16. The crushed product of the block copolymer according to the above 12 or 13, wherein the component (A) has a weight average molecular weight of 20,000 or more and 120,000 or less.

The crushed product of the block copolymer according to any one of the above items 12 to 16, wherein the component (B) has a weight average molecular weight of 140,000 or more and 1,000,000 or less.

The crushed product of the block copolymer according to any one of the above items 12 to 17, wherein the component (B) has a weight average molecular weight of 200,000 or more and 1,000,000 or less.

The crushed product of the block copolymer according to the above 12 or 13, wherein the component (B) has a weight average molecular weight of 30,000 or more and 200,000 or less.

The crushed product of the block copolymer according to any one of the above items 12 to 19, wherein the component (B) contains two polymer blocks mainly composed of a vinyl aromatic hydrocarbon monomer unit, and at least 1 A polymer block mainly composed of a monomer unit of a conjugated diene compound.

The crushed product of the block copolymer according to any one of the above 1 to 20, wherein the hydrogenation ratio H (mol%) of the unsaturated double bond based on the conjugated diene compound is 5% or more.

The crushed product of the block copolymer according to any one of the above 1 to 21, wherein the hydrogenation rate H (mol%) of the unsaturated double bond based on the conjugated diene compound is 90% or less.

An adhesive composition comprising 100 parts by mass of a polymer comprising the crushed product of the block copolymer according to any one of 1 to 22 above, 20 to 500 parts by mass of an adhesion-imparting agent, and a softening agent. 0 to 300 parts by mass.

According to the present invention, it is possible to provide an adhesive composition which is excellent in conveyability and which can be used for an adhesive composition to have solubility, low melt viscosity characteristics, low odor characteristics, and excellent balance of such characteristics. A fracture of the block copolymer of the article, and an adhesive composition comprising the fracture of the block copolymer.

Hereinafter, the form for carrying out the present invention (hereinafter referred to as "this embodiment") will be described in detail. The present invention is not limited to the embodiments described below, and various modifications can be made without departing from the spirit and scope of the invention.

In the present specification, the structural unit constituting the polymer is referred to as "~monomer unit", and when the material is described as a polymer, the "unit" is omitted and only "~ monomer" is described.

[Blocked product of block copolymer]

The crushed product of the block copolymer of the present embodiment contains at least one polymer block mainly composed of a vinyl aromatic hydrocarbon monomer unit, and at least one polymer mainly composed of a monomer unit of a conjugated diene compound. The block has a weight average molecular weight of 20,000 to 1,000,000 and satisfies the following requirements (a) to (c).

(a) The specific surface area is 0.000001 m ² /g or more and less than 0.3 m ² /g (hereinafter, also referred to as "required condition (a)"); (b) the pore radius is 1 to 100 μm. The cumulative pore volume of the pores is 0.05 mL/g or more and less than 1.0 mL/g (hereinafter, also referred to as "required condition (b)"); (c) the average pore radius is 0.00001 μm or more and 1.5. Below μm (the following is also the case of "required condition (c)").

In the present specification, the broken product of the block copolymer of the present embodiment is also referred to as a "crushed product".

The specific surface area of the block copolymers was broken aspect of this embodiment of 0.000001m ² / g or more and less than 0.3m ² / g, preferably 0.2m ² / g or less, more preferably 0.15m ² / g or less, Further preferably 0.1m ² / g or less, and more preferably 0.08m ² / g or less, and particularly preferably 0.05m ² / g or less. When the specific surface area is 0.000001 m ² /g or more, the crushed material having excellent solubility is obtained, and the adhesive composition containing the crushed material is excellent in adhesion characteristics and low odor characteristics, and the specific surface area is less than 0.3 m ^{2 .} /g is a crushed product excellent in solubility and transportability, and the adhesive composition containing the crushed material is excellent in adhesion characteristics.

The average pore diameter of the crushed product of the block copolymer of the present embodiment is 0.00001 μm or more and 1.5 μm or less, preferably 0.00005 μm or more, more preferably 0.0001 μm or more, further preferably 0.001 μm or more, and further preferably further. It is 0.005 μm or more, and particularly preferably 0.0085 μm or more. Further, the upper limit is preferably 1.0 μm or less, more preferably 0.1 μm or less, further preferably 0.05 μm or less, further preferably 0.025 μm or less, further preferably 0.02 μm or less, and particularly preferably 0.016 μm or less. When the average pore radius is 0.00001 μm or more, the crushed material having excellent solubility is obtained, and the adhesive composition obtained by using the crushed material is excellent in adhesion characteristics and low odor characteristics, and the average pore radius is obtained. When it is 1.5 μm or less, it is a crushed product excellent in solubility, and the adhesive composition using the crushed material is excellent in adhesion performance.

In the crushed product of the block copolymer of the present embodiment, the maximum value of the log differential pore indentation volume when the pore radius is 1 μm or more and 100 μm is divided by the log differential pore having a pore radius of 0.001 μm or more and less than 1 μm. The value obtained by injecting the maximum value of the volume [(the maximum value of the log differential pore indentation volume when the pore radius is 1 μm or more and 100 μm or less) / (log differential fine when the pore radius is 0.001 μm or more and less than 1 μm) The maximum value of the pore indentation volume) (hereinafter, the case where the value is only described as "Z") is preferably 0.1 or more and 6 or less. The Z of the crushed matter is preferably 0.25 or more, more preferably 0.3 or more, still more preferably 0.4 or more, still more preferably 0.5 or more, and still more preferably 0.6 or more. Further, it is more preferably 2 or less, still more preferably 1.5 or less, still more preferably 1.45 or less, still more preferably 1.35 or less, and still more preferably 1.0 or less. When the value (Z) is 0.1 or more, the crushed material having excellent solubility is obtained, and the adhesive composition obtained from the crushed material is excellent in low odor characteristics and adhesive properties, and the value (Z) is obtained. When it is 6 or less, it becomes a crushing material which is excellent in solubility, and becomes an adhesive composition.

The cumulative pore volume of the crushed product of the block copolymer of the present embodiment is preferably 0.0001 mL/g or more and 1.2 mL/g or less. The cumulative pore volume of the crushed material is preferably 0.01 mL/g. Further, it is preferably 0.05 mL/g or more, more preferably 0.1 mL/g or more, and still more preferably 0.2 mL/g or more. Further, it is more preferably less than 0.6 mL/g, still more preferably 0.5 mL/g or less, and still more preferably less than 0.4 mL/g. When the cumulative pore volume is 0.0001 mL/g or more, the crushed material having excellent solubility is obtained, and the adhesive composition obtained by using the crushed material is excellent in low odor characteristics, and the cumulative pore volume is 1.2. It is below the mL/g, and it becomes a crushing substance excellent in solubility.

In the fracture product of the block copolymer of the present embodiment, the cumulative pore volume of the pores having a pore radius of from 1 μm to 100 μm is 0.05 mL/g or more and less than 1.0 mL/g, preferably 0.08 mL/g. the above. When the cumulative pore volume is 0.05 ml/g or more, the crushed material having excellent solubility is obtained, and the adhesive composition obtained by using the crushed material is excellent in low odor characteristics. When the cumulative pore volume is less than 1.0 mL/g, it becomes a crushed product excellent in solubility.

In the crushed product of the block copolymer of the present embodiment, the cumulative pore volume of the pores having a pore radius of 1 μm to 100 μm is divided by the cumulative pore volume of the pores having a pore radius of 0.001 μm or more and 100 μm or less. The value obtained (the cumulative pore volume of the pores having a pore radius of from 1 μm to 100 μm) / (the cumulative pore volume of the pores having a pore radius of from 0.001 μm to 100 μm) is preferably 0.3 or more, and Good is below 0.8. The lower limit of the value is more preferably 0.4 or more, further preferably 0.45 or more, more preferably 0.5 or more, and the upper limit is more preferably 0.77 or less, further preferably 0.72 or less, further preferably 0.69 or less, and particularly preferably 0.66 or less. . The value obtained by dividing the cumulative pore volume of the pores having a pore radius of 1 to 100 μm by the cumulative pore volume of the pores having a pore radius of 0.001 μm or more and 100 μm or less ((the pore radius is 1 μm~) The cumulative pore volume of the fine pores of 100 μm/(the cumulative pore volume of the pores having a pore radius of 0.001 μm to 100 μm) is 0.3 or more, and is a crushed product which is more excellent in solubility than the crushed material, and includes the same. When the adhesive composition is excellent in low odor characteristics, the above-mentioned value is 0.8 or less, and it is a crushed material excellent in solubility.

Specific surface area of the fractured product of the block copolymer, average pore radius, [(fine pore radius 1 The maximum value of the log differential pore indentation volume when μm or more and 100 μm or less) / (the maximum value of the log differential pore indentation volume when the pore radius is 0.001 μm or more and less than 1 μm)], the cumulative pore volume, Cumulative pore volume of pores having a pore radius of 1 to 100 μm, cumulative pore volume of pores having a pore radius of 1 to 100 μm divided by cumulative pores of pores having a pore radius of 0.001 μm or more and 100 μm The value obtained by the volume ((the cumulative pore volume of the pores having a pore radius of 1 μm to 100 μm) / (the cumulative pore volume of the pores having the pore radius of 0.001 μm to 100 μm) can be adjusted by the following The various conditions of the structure or the production method of the block copolymer are controlled within the above range, and are measured by the methods described in the following examples.

[block copolymer]

The block copolymer constituting the crushed product of the present embodiment contains at least one polymer block mainly composed of a vinyl aromatic hydrocarbon monomer unit (hereinafter also referred to as "polymer block Ar") and at least one A polymer block mainly composed of a conjugated diene compound monomer unit (hereinafter also referred to as "polymer block D"), and having a weight average molecular weight of 20,000 or more and 1,000,000 or less, preferably 50,000 or more, more preferably It is 70,000 or more. Further, the upper limit is preferably 500,000 or less.

The weight average molecular weight of the block copolymer is 20,000 or more, and the retention, adhesion, and productivity are excellent, and the weight average molecular weight of the block copolymer is 1,000,000 or less, thereby obtaining excellent low melt viscosity characteristics. The block copolymer and adhesive composition. Further, the weight average molecular weight of the block copolymer can be determined by the method described in the examples.

When a plurality of polymer blocks Ar and/or D are present in the block copolymer, the weight average molecular weight, composition, and structure of each of the polymer blocks Ar and D may be the same or different.

In the present specification, the term "the vinyl aromatic hydrocarbon monomer unit as a main component" means that the content of the vinyl aromatic hydrocarbon monomer unit in the polymer block is 60% by mass or more, preferably 80% by mass or more. More preferably, it is 90% by mass or more, and further preferably 95% by mass. on.

In the present specification, the term "the conjugated diene compound monomer unit as a main component" means that the content of the conjugated diene compound monomer unit in the polymer block is 60% by mass or more, preferably 80%. The mass% or more is more preferably 90% by mass or more, and still more preferably 95% by mass or more.

The structure of the block copolymer is not particularly limited, and examples thereof include the following formulas (i) to (vi).

(Ar-D) _n (i)

D-(Ar-D) _n (ii)

Ar-(D-Ar) _n (iii)

Ar-(D-Ar) _n -X (iv)

[(Ar-D) _k ] _m -X (v)

[(Ar-D) _k -Ar] _m -X (vi)

(In the above formulas (i) to (vi), Ar represents a polymer block (Ar) mainly composed of a vinyl aromatic hydrocarbon monomer unit, and D represents a polymer mainly composed of a monomer unit of a conjugated diene compound. Block (D), X represents a residue of a coupling agent or a residue of a polymerization initiator such as polyfunctional organic lithium, and m, n and k represent an integer of 1 or more, preferably an integer of 1 to 6, with respect to the presence of plural In the case of Ar, the type and molecular weight of the vinyl aromatic hydrocarbon monomer may be the same or different. For the case where there are a plurality of D, the type and molecular weight of the conjugated diene compound monomer may be the same or different. ).

The content of the vinyl aromatic hydrocarbon monomer unit in the block copolymer of the present embodiment is not particularly limited, but is preferably 5% by mass or more, more preferably 8% by mass or more, and still more preferably 10% by mass or more. Further, the content of the vinyl aromatic hydrocarbon monomer unit in the block copolymer is not particularly limited, but is preferably 90% by mass or less, more preferably 70% by mass or less, still more preferably 50% by mass or less, and furthermore It is preferably 45 mass% or less, more preferably 40 mass% or less, and further preferably less than 20 mass%. By the B in the block copolymer of the present embodiment The content of the alkenyl aromatic hydrocarbon monomer unit is in the above range, and there is a tendency to obtain a block copolymer and an adhesive composition which have excellent adhesion properties and excellent balance. In particular, when the content of the vinyl aromatic hydrocarbon monomer unit is 5% by mass or more, there is a tendency to obtain a block copolymer and an adhesive composition having excellent adhesion and retention. In addition, the content of the vinyl aromatic hydrocarbon monomer unit is 90% by mass or less, and the block copolymer and the adhesive composition having excellent viscosity tend to be obtained.

When the fracture product of the block copolymer is used for a sanitary material, the content of the vinyl aromatic hydrocarbon monomer unit in the block copolymer is preferably 10% by mass or more, more preferably 20% by mass or more. Further, it is preferably 25% by mass or more. Moreover, it is preferably 70% by mass or less, more preferably 50% by mass or less, further preferably 45% by mass or less, and still more preferably 40% by mass or less. When the content of the vinyl aromatic hydrocarbon monomer unit in the block copolymer is 10% by mass or more, there is a tendency to obtain a block copolymer and an adhesive composition having excellent adhesion and retention. In addition, when the content of the vinyl aromatic hydrocarbon monomer unit is 70% by mass or less, a block copolymer having an excellent viscosity and a binder composition tend to be obtained.

When the crushed product of the block copolymer is used for a tape or a marking application, the content of the vinyl aromatic hydrocarbon monomer unit in the block copolymer is preferably 5% by mass or more, more preferably 8% by mass or more. Further, it is preferably 10% by mass or more. Further, it is preferably 40% by mass or less, more preferably 30% by mass or less, further preferably 25% by mass or less, and still more preferably less than 20% by mass. When the content of the vinyl aromatic hydrocarbon monomer unit in the block copolymer is 5% by mass or more, there is a tendency to obtain a block copolymer and an adhesive composition having excellent adhesion and retention. In addition, the content of the vinyl aromatic hydrocarbon monomer unit is 40% by mass or less, and the block copolymer and the adhesive composition having excellent viscosity tend to be obtained.

Here, in the case where the crushed product is a crushed product of the block copolymer composition containing the following component (A) and component (B), the so-called vinyl aromatic hydrocarbon monomer in the block copolymer The content of the element is not the value of each component, and is the average content of the block copolymer, that is, the average value of each component. The content of the vinyl aromatic hydrocarbon monomer unit in the block copolymer can be measured by the method described in the following examples.

Further, in the block copolymer of the present embodiment, the conjugated diene compound monomer unit (based on the unsaturated double bond of the conjugated diene compound) contained in the polymer block mainly composed of the conjugated diene compound monomer ) can also be hydrogenated. The hydrogenation ratio of the conjugated diene compound monomer unit is preferably 5 mol% or more, and preferably 90 mol% or less. The hydrogenation ratio of the conjugated diene compound monomer unit is more preferably 10 mol% or more, still more preferably 15 mol% or more, still more preferably 20 mol% or more. The hydrogenation rate is 5 mol% or more, and there is a tendency that the holding force, the viscosity, and the adhesion are excellent. Further, the hydrogenation ratio of the conjugated diene compound monomer unit is more preferably 80 mol% or less, further preferably 70 mol% or less, and still more preferably 60 mol% or less. The hydrogenation ratio is 90 mol% or less, and the low viscosity property tends to be excellent.

In addition, the hydrogenation ratio of the conjugated diene compound monomer unit is preferably 10% by mole or more and 80% by mole or less, more preferably 15% by mole or more and 70% by mole or less, and still more preferably 20% by mole or more and 60% by mole or less. When the hydrogenation ratio of the conjugated diene compound monomer unit is within the above range, the hydrogenated block copolymer and the adhesive composition which are excellent in adhesion characteristics or low melt viscosity characteristics and excellent in balance are obtained. tendency. The hydrogenation ratio of the monomer unit of the conjugated diene compound in the hydrogenated block copolymer can be measured by the method described in the examples.

In the block copolymer, the upper limit of the amount of the vinyl bond of the conjugated diene compound monomer unit (before hydrogenation) is preferably 80 mol% or less, more preferably 70 mol% or less. It is preferably 60 mol% or less, and more preferably 50 mol% or less. In addition, the lower limit of the amount of vinyl bonds of the monomer unit of the conjugated diene compound before hydrogenation is preferably 5 mol% or more, more preferably 8 mol% or more, further preferably 10 mol% or more, and still more preferably 25 mol%. The above is more preferably 30 mol% or more. More specifically, the block copolymer has a vinyl bond amount of a conjugated diene compound monomer unit before hydrogenation It is preferably 5 mol% or more and 80 mol% or less, preferably 8 mol% or more and 70 mol% or less, preferably 10 mol% or more and 60 mol% or less. When the amount of the vinyl bond of the conjugated diene compound monomer unit is within the above range, there is a tendency to obtain properties excellent in productivity, viscosity, and adhesion.

Here, in the case where the crushed product is a crushed product of the block copolymer composition containing the component (A) and the component (B) described below, the vinyl bond amount of the monomer unit of the conjugated diene compound ( In the case of hydrogenation, the amount of vinyl bond of the monomer unit of the conjugated diene compound before hydrogenation, not the value of each component, is the amount of vinyl bond as a whole of the block copolymer, that is, each component The average of the amount of vinyl bond. Further, the "vinyl bond amount" is a total mol amount of a conjugated diene compound monomer unit introduced by a 1,2-bond and a 3,4-bond before hydrogenation, with respect to a 1,2-bond. The ratio of the total molar amount of the monomer unit of the conjugated diene compound in the component (A) and the component (B) introduced by the bonding form of the 3,4-bond and 1,4-bond. The amount of vinyl bond of the conjugated diene compound monomer unit can be measured by nuclear magnetic resonance spectroscopy (NMR), and specifically, it can be measured by the method described in the following examples.

In the case of hydrogenation, after hydrogenation, the unhydrogenated 1,2-bond, hydrogenated 1,2-bond, unhydrogenated 3,4-bond and hydrogenated 3,4-bonded conjugate are introduced. The total mol amount of the diene compound monomer unit is relative to the unhydrogenated 1,2-bond, the hydrogenated 1,2-bond, the unhydrogenated 3,4-bond, the hydrogenated 3,4-bond, and The ratio of the total mol amount of the conjugated diene compound monomer unit introduced by the hydrogenated 1,4-bond and the hydrogenated 1,4-bond bond pattern to the conjugated diene compound monomer unit before hydrogenation The amount of vinyl linkage is equal. In the case where the crushed material is a crushed product containing the hydrogenated block copolymer composition, the amount of vinyl bond of the monomer unit of the conjugated diene compound before hydrogenation is not the value of each component, and is used as a hydrogenated block. The amount of vinyl bond of the copolymer as a whole, that is, the average amount of vinyl bonds of each component. Therefore, the amount of vinyl bond of the monomer unit of the conjugated diene compound before hydrogenation can be measured by nuclear magnetic resonance spectroscopy (NMR) using a hydrogenated block copolymer composition, specifically, The measurement was carried out by the method described in the following examples. Block copolymer In the case of hydrogenation, the content of the vinyl aromatic hydrocarbon monomer unit and the weight average molecular weight are substantially the same values before and after the hydrogenation, and therefore the value after hydrogenation is employed.

Further, in the hydrogenation step, the conjugated bond of the vinyl aromatic hydrocarbon monomer unit may be hydrogenated, and the conjugated bond of all the vinyl aromatic hydrocarbon monomer units may be maintained from the viewpoint of holding force or adhesion. The hydrogenation rate is preferably 30 mol% or less, more preferably 10 mol% or less, still more preferably 3 mol% or less.

[Block copolymer composition]

The crushed product of the present embodiment preferably comprises a block copolymer having two different structures of the following components (A) and (B) from the viewpoint of improving the balance between the adhesive properties and the low melt viscosity characteristics. A fracture of the block copolymer composition. In this case, the ratio of the weight average molecular weight of the component (A) to the component (B) [(weight average molecular weight of the component (B)) / (weight average molecular weight of the component (A))] is preferably from 1.3 to 10.

The component (A) contains at least one polymer block (Ar) mainly composed of a vinyl aromatic hydrocarbon monomer unit and at least one polymer block mainly composed of a monomer unit of a conjugated diene compound ( The block polymer of D), wherein the weight average molecular weight is preferably 20,000 or more and 500,000 or less, and the component (B) contains at least one polymer block (Ar) mainly composed of a vinyl aromatic hydrocarbon monomer unit. A block polymer of at least one polymer block (D) mainly composed of a conjugated diene compound monomer unit, and the weight average molecular weight is preferably 30,000 or more and 1,000,000 or less.

When a plurality of polymer blocks Ar and/or D are present in the block copolymer of the component (A) and/or the component (B), the weight average molecular weight, composition and structure of each of the polymer blocks Ar and D Can be the same or different.

The content of each of the component (A) and the component (B) in the block copolymer fracture is preferably 20% by mass or more and 90% by mass or less of the component (A), and the component (B) is 10% by mass or more and 80%. The mass% or less is more preferably the component (A) is 30% by mass or more and 85% by mass or less, and the component is (B) is 15% by mass or more and 70% by mass or less, and further preferably, the component (A) is 35 mass% or more and 80 mass% or less, and the component (B) is 20 mass% or more and 65 mass% or less, and further More preferably, the component (A) is 40% by mass or more and 75% by mass or less, and the component (B) is 25% by mass or more and 60% by mass or less.

When the content of the component (A) and the component (B) is within the above range, the fracture property and the adhesion of the block copolymer which are excellent in low melt viscosity characteristics and adhesion characteristics are excellent, and the balance is also good. Composition.

The content of the component (A) and the component (B) can be controlled within the above range by adjusting various conditions of the production method described below. Further, the contents of the component (A) and the component (B) can be measured by the methods described in the following examples. Further, in the case of hydrogenating the block copolymer, the values of the contents of the component (A) and the component (B) are substantially the same values before and after the hydrogenation, but the values after hydrogenation are employed.

The ratio of the weight average molecular weight of the component (B) to the weight average molecular weight of the component (A) (the weight average molecular weight of the component (B)) / (the weight average molecular weight of the component (A)) is preferably 1.3 or more and 10 or less. More preferably, it is 1.5 or more and 8.0 or less, More preferably, it is 1.8 or more and 5.0 or less. When the ratio of the weight average molecular weight of the component (B) to the weight average molecular weight of the component (A) is within the above range, a block having excellent low-melting viscosity characteristics and excellent adhesion properties, and excellent balance is also obtained. A fracture of the copolymer and an adhesive composition. The ratio of the content of the component (A) and the component (B), the weight average molecular weight, and the weight average molecular weight can be controlled within the above range by adjusting various conditions of the production method described below. Further, the ratio of the content of the component (A) and the component (B), the weight average molecular weight, and the weight average molecular weight can be measured by the methods described in the following examples. Hereinafter, each component will be described in more detail.

[block copolymer]

(ingredient (A))

Component (A) preferably contains at least one monomer unit having a vinyl aromatic hydrocarbon unit as a main component The polymer block (Ar) and at least one polymer block (D) mainly composed of a monomer unit of a conjugated diene compound. Further, the component (A) is more preferably a polymer block (Ar) mainly composed of a vinyl aromatic hydrocarbon monomer unit and at least one polymer block mainly composed of a monomer unit of a conjugated diene compound ( D), and the polymer block Ar is one block copolymer.

The weight average molecular weight of the block copolymer of the component (A) is preferably 20,000 or more and 500,000 or less, more preferably 30,000 or more, still more preferably 40,000 or more, still more preferably 50,000 or more, and still more preferably 70,000 or more. Further, the lower limit is more preferably less than 200,000, still more preferably 175,000 or less, still more preferably 150,000 or less, and still more preferably 120,000 or less.

The weight average molecular weight of the component (A) is 20,000 or more, and the productivity is excellent, and the weight average molecular weight of the component (A) is 500,000 or less, thereby obtaining a block copolymer having excellent low melt viscosity characteristics. Broken material and adhesive composition. Further, the weight average molecular weight of the component (A) can be determined by the method described in the examples.

In the case of use for a tape or a mark, the weight average molecular weight of the component (A) is preferably 40,000 or more and 500,000 or less, more preferably 70,000 or more and 500,000 or less, further preferably 40,000 or more and less than 200,000. In the case of use for a sanitary material, the weight average molecular weight of the component (A) is preferably 20,000 or more and 175,000 or less, more preferably 20,000 or more and 150,000 or less, and still more preferably 20,000 or more and 120,000 or less.

The structure of the component (A) is not particularly limited, and examples thereof include the following formulas (i) to (vi).

(Ar-D) _n (i)

D-(Ar-D) _n (ii)

Ar-(D-Ar) _n (iii)

Ar-(D-Ar) _n -X (iv)

[(Ar-D) _k ] _m -X (v)

[(Ar-D) _k -Ar] _m -X (vi)

(In the above formulas (i) to (vi), Ar represents a polymer block (Ar) mainly composed of a vinyl aromatic hydrocarbon monomer unit, and D represents a polymer mainly composed of a monomer unit of a conjugated diene compound. Block (D), X represents a residue of a coupling agent or a residue of a polymerization initiator such as polyfunctional organic lithium, and m, n and k represent an integer of 1 or more, preferably an integer of 1 to 6, with respect to the presence of plural In the case of Ar, the type or molecular weight of the vinyl aromatic hydrocarbon monomer may be the same or different. For the case where there are a plurality of D, the type or molecular weight of the conjugated diene compound monomer may be the same or different. ).

The component (A) is preferably a block copolymer in which Ar is one of the above formulas (i) to (vi), and more preferably a block copolymer represented by Ar-D or D-Ar-D. By having the above structure of the component (A), it is possible to obtain a fracture product and an adhesive composition of a block copolymer which has excellent low melt viscosity characteristics, adhesion, and viscosity, and which are excellent in balance. The tendency.

(ingredient (B))

The component (B) is preferably a polymer block containing at least one polymer block (Ar) mainly composed of a vinyl aromatic hydrocarbon monomer unit and at least one polymer block mainly composed of a conjugated diene compound monomer unit. (D). Further, the component (B) is more preferably a polymer block (Ar) containing at least two vinyl aromatic hydrocarbon monomer units as a host and at least one polymer mainly composed of a conjugated diene compound monomer unit. The block (D) and the polymer block (Ar) in the component (B) are preferably two or more.

The weight average molecular weight of the block copolymer of the component (B) is preferably 30,000 or more and 1,000,000 or less, more preferably 50,000 or more, still more preferably 70,000 or more. Further, it is more preferably 500,000 or less. By the weight average molecular weight of the component (B) of 30,000 or more, a crushed product and a binder composition of the block copolymer having excellent retention or adhesion are obtained, and, by weight average of the component (B) The molecular weight is 1,000,000 or less, and a fracture product and an adhesive composition of a block copolymer having excellent low melt viscosity characteristics are obtained. Furthermore, the weight average molecular weight of the component (B) can be determined by the method described in the examples. Find out.

When the crushed product of the block copolymer is used for a tape or a mark or the like, the weight average molecular weight of the block copolymer of the component (B) is preferably 70,000 or more, more preferably 100,000 or more, and still more preferably 140,000. The above is more preferably 170,000 or more, and particularly preferably 200,000 or more. Further, the weight average molecular weight of the block copolymer of the component (B) is preferably 1,000,000 or less, more preferably 850,000 or less, still more preferably 650,000 or less, still more preferably 500,000 or less. By the weight average molecular weight of the component (B) of 70,000 or more, the crushed product and the adhesive composition of the block copolymer having excellent retention or adhesion are obtained, and the weight average by the component (B) The molecular weight is 1,000,000 or less, and a fracture product and an adhesive composition of a block copolymer having excellent low melt viscosity characteristics are obtained.

When the fracture product of the block copolymer is used for a sanitary material, the weight average molecular weight of the block copolymer of the component (B) is preferably 30,000 or more, more preferably 50,000 or more, still more preferably 70,000 or more. More preferably, it is 90,000 or more, and more preferably 100,000 or more. Further, the weight average molecular weight of the block copolymer of the component (B) is preferably 850,000 or less, more preferably 650,000 or less, still more preferably 500,000 or less, still more preferably 300,000 or less, and still more preferably 200,000 or less. By the weight average molecular weight of the component (B) of 30,000 or more, a crushed product and a binder composition of the block copolymer having excellent retention or adhesion are obtained, and, by weight average of the component (B) The molecular weight is 850,000 or less, and a fracture product and an adhesive composition of a block copolymer having excellent low melt viscosity characteristics are obtained.

In addition, the structure of the component (B) is not particularly limited, and examples thereof include the following formulas (vii) to (xiii).

(Ar-D) _e (vii)

D-(Ar-D) _e (viii)

Ar-(D-Ar) _g (ix)

[Ar-(D-Ar) _g ] _f -X (x)

[D-(Ar-D) _g ] _f -X (xi)

[(Ar-D) _g ] _f -X (xii)

[(Ar-D) _g -Ar] _f -X (xiii)

(In the above formulas (vii) to (xiii), Ar represents a polymer block (Ar) mainly composed of a vinyl aromatic hydrocarbon monomer unit, and D represents a polymer mainly composed of a monomer unit of a conjugated diene compound. Block (D), X represents a residue of a coupling agent or a residue of a polymerization initiator such as polyfunctional organic lithium, and e and f represent an integer of 2 or more, g represents an integer of 1 or more, and g is preferably 6 or less. A positive integer, the type or molecular weight of the vinyl aromatic hydrocarbon monomer may be the same or different with respect to Ar in the case of a plurality of Ar, and the type of the conjugated diene compound monomer or the case where a plurality of D are present or The molecular weights may be the same or different).

The component (B) is preferably a block copolymer containing two or more Ar in the formulas (vii) to (xiii), more preferably a block copolymer of two or two, or a formula (xi) or a formula (xi). Xii) wherein g=1, and further preferably comprises from the formulas Ar-D-Ar, (Ar-D) ₂ X, D-Ar-D-Ar, D-Ar-D-Ar-D, [D- (Ar-D)] ₂ X, [D-(Ar-D)] ₃ -X, [(Ar-D)] ₃ -X, [D-(Ar-D)] ₄ -X, and/or [ (Ar-D)] A block copolymer represented by ₄ -X. When the component (B) contains the above block copolymer, there is a tendency to obtain a fracture product and a binder composition of a block copolymer excellent in productivity or adhesion properties.

The component (B) is preferably a polymer block containing two vinyl aromatic hydrocarbons as a main component and at least one polymer mainly composed of a conjugated diene compound, from the viewpoint of retention and adhesion. Block copolymers of blocks.

Further, it is more preferred that the block copolymer of the component (B) has a weight average molecular weight of 140,000 or more and contains two polymer blocks mainly composed of a vinyl aromatic hydrocarbon and at least one conjugated diene compound. A block copolymer of a polymer block as a host. The block copolymer containing two polymer blocks mainly composed of a vinyl aromatic hydrocarbon and at least one polymer block mainly composed of a conjugated diene compound is not particularly limited, and examples thereof include, for example, formula Ar-D-Ar, (Ar -D) 2 X, D-Ar-D-Ar, D-Ar-D-Ar-D, D- (Ar-D) 2 X, or two or more of these and a mixture or the like.

The block copolymer constituting the crushed product of the block copolymer of the present embodiment is preferably a block copolymer composition comprising the component (A) and the component (B), and the component (A) contains a vinyl aromatic group. a hydrocarbon monomer unit as a main polymer block (Ar) and at least one polymer block (D) mainly composed of a conjugated diene compound monomer unit, and the polymer block Ar is one block a copolymer, the component (B) comprising at least two polymer blocks (Ar) mainly composed of a vinyl aromatic hydrocarbon monomer unit and at least one polymer block mainly composed of a monomer unit of a conjugated diene compound (D).

[Method for Producing Broken Material of Block Copolymer]

The crushed product of the block copolymer is not particularly limited, and for example, it can be produced by sequentially performing a polymerization step in a hydrocarbon solvent using an organolithium compound as a polymerization initiator to at least a conjugated diene. Polymerization of a compound monomer with a vinyl aromatic hydrocarbon monomer to obtain a polymer; a solvent removal step of desolvating a solvent comprising a solution of the block copolymer; and a physicochemical step of desolvation The block copolymer is subjected to crushing and physicalization. Further, after the polymerization step, a hydrogenation step of hydrogenating the double bond in the monomer unit of the conjugated diene compound of the obtained polymer may be used, and the hydrogenation step is preferably after the polymerization step and before the solvent removal step. get on. The weight average molecular weight of the block copolymer can be adjusted, for example, by controlling the type or addition amount of the coupling agent described below. Further, the addition amount and the number of additions of the polymerization initiator described below are controlled and added in several times, whereby the weight average molecular weight can also be adjusted. Further, by controlling the addition amount of the deactivator described below, the deactivation step is carried out once, and the polymerization reaction is further continued, whereby the weight average molecular weight can also be adjusted.

In the case where the block copolymer is a block copolymer composition comprising a block copolymer having a different structure of the component (A) and the component (B), the component (A) and the component (B) may be separately manufactured, and thereafter Mixing can also be carried out simultaneously. Ratio of weight average molecular weight and weight average molecular weight of component (A) to component (B) when component (A) and component (B) are simultaneously produced The content can be adjusted, for example, by controlling the type or amount of the coupling agent described below. Further, by controlling the addition amount and the number of additions of the polymerization initiator described below, and adding it several times, the ratio of the weight average molecular weight and the weight average molecular weight of the component (A) to the component (B) can also be adjusted. . Further, by controlling the addition amount of the deactivator described below, the deactivation step is performed once, and the polymerization reaction is further continued, whereby the ratio of the weight average molecular weight and the weight average molecular weight of the component (A) to the component (B) can also be adjusted. . Hereinafter, each step will be described.

(aggregation step)

The polymerization step is a step of polymerizing a monomer containing at least a conjugated diene compound monomer and a vinyl aromatic hydrocarbon monomer in a hydrocarbon solvent using an organolithium compound as a polymerization initiator to obtain a polymer.

The polymerization temperature is usually from 10 to 150 ° C, preferably from 30 to 130 ° C, more preferably from 40 to 100 ° C. The polymerization pressure is not particularly limited as long as it is carried out within a pressure range in which the monomer amount and the solvent are sufficiently maintained in the liquid phase within the above polymerization temperature range. The polymerization time varies depending on the conditions, and is usually within 48 hours, preferably from 0.5 to 10 hours.

<hydrocarbon solvent>

It is preferred to use a hydrocarbon solvent in the polymerization step as described above. The hydrocarbon solvent is not particularly limited, and examples thereof include aliphatic hydrocarbons such as butane, pentane, hexane, isopentane, heptane, and octane; cyclopentane, methylcyclopentane, and cyclohexane. An alicyclic hydrocarbon such as methylcyclohexane or ethylcyclohexane; an aromatic hydrocarbon such as benzene, toluene, ethylbenzene or xylene; and the like. The hydrocarbon solvent may be used alone or in combination of two or more.

<Polymerization initiator>

In the polymerization step, it is preferred to use at least an organolithium compound as a polymerization initiator. The organolithium compound is not particularly limited, and examples thereof include an organic monolithium compound in which one or more lithium atoms are bonded to a molecule, an organic dilithium compound, and an organic polylithium compound. More specifically, ethyl lithium, n-propyl lithium, isopropyl lithium, n-butyl lithium, second butyl lithium, t-butyl lithium, hexamethylene dilithium, butadienyl group Dilithium Pentadienyl dilithium and the like. The polymerization initiator may be used alone or in combination of two or more.

The polymerization initiator may also be added to the reaction solution several times. Thereby, a composition comprising a plurality of block copolymers having a weight average molecular weight or a structure different can be obtained at one time.

<Monomer for polymerization>

The conjugated diene compound single system has a diene of one pair of conjugated double bonds. The conjugated diene compound monomer is not particularly limited, and examples thereof include 1,3-butadiene, 2-methyl-1,3-butadiene (isoprene), and 2,3-di. Methyl-1,3-butadiene, 1,3-pentadiene, 2-methyl-1,3-pentadiene, 1,3-hexadiene, and the like. Among them, preferred are 1,3-butadiene and isoprene. Further, from the viewpoint of improving the retaining power of the adhesive composition, 1,3-butadiene is more preferable. The conjugated diene compound monomer may be used alone or in combination of two or more.

The vinyl aromatic hydrocarbon monomer is not particularly limited, and examples thereof include styrene, α-methylstyrene, p-methylstyrene, divinylbenzene, stilbene, and N,N-. Dimethyl-p-aminoethylstyrene, N,N-diethyl-p-aminoethylstyrene, and the like. Among them, styrene is preferred in terms of economy. The vinyl aromatic hydrocarbon monomer may be used singly or in combination of two or more.

The block copolymer may further comprise a monomer unit other than a vinyl aromatic hydrocarbon monomer unit and a conjugated diene compound monomer unit, and a vinyl aromatic hydrocarbon monomer and a conjugated diene compound single in the polymerization step. Other monomers copolymerizable with the above monomers may also be used in vitro.

In the polymerization step, the polymerization rate is adjusted, the microstructure of the polymerized conjugated diene compound monomer unit (the ratio of cis, trans, vinyl), and the conjugated diene compound monomer and ethylene are controlled. For the purpose of adjusting the reaction ratio of the aromatic hydrocarbon-containing monomer, etc., a specific polar compound or a randomizer can be used.

The polar compound or the randomizer is not particularly limited, and examples thereof include ethers such as tetrahydrofuran, diethylene glycol dimethyl ether, and diethylene glycol dibutyl ether; and triethylamine and tetramethyl-ethylidene Amines such as amines; thioethers, phosphines, phosphoniumamines, alkylbenzenesulfonates, potassium or sodium alkoxides, and the like.

<coupling agent>

In the polymerization step, a solution containing a vinyl aromatic-conjugated diene block copolymer having an active terminal may be added in an amount of less than 1 mole equivalent relative to the above-mentioned active terminal. A coupling agent for the structure represented by X in the formulae (iv) to (vi) and (x) to (xiii).

The coupling agent to be added is not particularly limited, and any of two or more functional coupling agents can be used. The bifunctional coupling agent is not particularly limited, and examples thereof include a bifunctional halogenated decane such as dichlorodecane, monomethyldichlorodecane or dimethyldichlorodecane; diphenyldimethoxydecane and a bifunctional alkoxydecane such as phenyldiethoxydecane, dimethyldimethoxydecane or dimethyldiethoxydecane; dichloroethane, dibromoethane, dichloromethane, dibromomethane And other bifunctional halogenated alkanes; dichlorotin, monomethyldichlorotin, dimethyldichlorotin, monoethyldichlorotin, diethyldichlorotin, monobutyltin dichloride, dibutyl a bifunctional tin halide such as chlorotin; dibromobenzene, benzoic acid, CO, 2-chloropropene, and the like.

The trifunctional coupling agent is not particularly limited, and examples thereof include a trifunctional halogenated alkane such as trichloroethane or trichloropropane; a trifunctional halogenated decane such as methyltrichlorodecane or ethyltrichlorodecane; a trifunctional alkoxydecane such as a methoxymethoxydecane, a phenyltrimethoxydecane or a phenyltriethoxydecane; and the like.

The tetrafunctional coupling agent is not particularly limited, and examples thereof include a tetrafunctional halogenated alkane such as carbon tetrachloride, carbon tetrabromide or tetrachloroethane, and a tetrafunctional halogenated decane such as tetrachlorodecane or tetrabromodecane. a tetrafunctional alkoxydecane such as tetramethoxynonane or tetraethoxysilane; a tetrafunctional tin halide such as tetrachlorotin or tetrabromotin; and the like.

The coupling agent having five or more functional groups is not particularly limited, and examples thereof include 1,1,1,2,2-pentachloroethane, perchloroethane, pentachlorobenzene, perchlorobenzene, and octabromodiphenyl ether. , decabromodiphenyl ether and the like. In addition to this, a epoxidized soybean oil, a 2- to 6-functional epoxy group-containing compound, a carboxylic acid ester, or a divinylbenzene-based polyethylene compound can also be used. The coupling agent may be used alone or in combination of two or more.

Among the above, from the viewpoint of color tone and suppression of adverse effects on equipment, a non-halogen coupling agent is preferred. Further, from the viewpoint of productivity or suppression of adverse effects on equipment, an epoxy group-containing compound or alkoxydecane is preferred.

If the coupling agent is added to the solution containing the aromatic vinyl-conjugated diene block copolymer having an active terminal as described above, the coupling group is added in an amount of less than 1 mole equivalent to the active terminal. In one of the block copolymers of the vinyl aromatic-conjugated diene block copolymer having an active terminal, the living terminals are bonded to each other via a residue of the coupling agent. Then, the remaining portion of the vinyl aromatic-conjugated diene block copolymer having the active terminal remains in the solution in an unreacted state. In the reaction using these coupling agents, the coupling ratio can be controlled by preparing the type or amount of the coupling agent or the like.

The polymerization method to be carried out in the polymerization step in the method for producing a polymer of the present embodiment is not particularly limited, and a known method can be applied. For example, Japanese Patent Publication No. Sho 36-19286, Japanese Patent Special Publication No. Japanese Patent Publication No. Sho 46-32415, Japanese Patent Publication No. Sho 49-36957, Japanese Patent Publication No. Sho-48-2423, Japanese Patent Publication No. Sho 48-4106, Japanese Patent Special Publication No. Sho. The method described in Japanese Laid-Open Patent Publication No. SHO-60-186518, and the like.

<inactivation agent>

In the polymerization step, an inactivating agent may also be added. The deactivator is not particularly limited, and water or an alcohol or the like is known. Among them, from the viewpoint of the efficiency of deactivation, an alcohol is preferred. The deactivating agent can also be added at any point in the polymerization step. If the amount of the deactivator added is less than 100 mol% of the active end, the conjugated diene compound monomer and/or the vinyl aromatic hydrocarbon monomer may be further added after the addition of the deactivator. Thereby, the polymerization reaction of the unactivated active terminal with the conjugated diene compound monomer and/or the vinyl aromatic hydrocarbon monomer is continued, and a polymer solution containing polymers of different molecular weights can be obtained.

Further, a block copolymer comprising two different structures having the component (A) and the component (B) In the case of the block copolymer composition, the component (A) and the component (B) can be controlled by adjusting the amount of the molar amount of the deactivator relative to the addition amount of the polymerization initiator in the deactivation step. content. The more the amount of the molar amount of the deactivator added, the more the content of the component (A) becomes, and the smaller the amount of the molar amount of the deactivator is, the less the content of the component (B) becomes.

Further, after the addition of the deactivator, the conjugated diene compound monomer and/or the vinyl aromatic hydrocarbon monomer are added to continue the polymerization reaction, whereby the weight average molecular weight of the component (A) and the component (B) can be controlled. The ratio of the weight average molecular weight. Specifically, there is a tendency that after the addition of the deactivator, the amount of the conjugated diene compound monomer and/or the vinyl aromatic hydrocarbon monomer to be added increases, and the weight average molecular weight of the component (B) changes. The larger the amount, the larger the ratio of the weight average molecular weight becomes.

(hydrogenation step)

The method of producing the block copolymer may also comprise a hydrogenation step. The hydrogenation step is a step of subjecting the double bond in at least the conjugated diene compound monomer of the polymer obtained in the polymerization step to a hydride by a hydrogenation reaction. Specifically, hydrogenation can be carried out in an inert solvent in the presence of a hydrogenation catalyst to obtain a hydrogenated block copolymer solution. At this time, the hydrogenation rate of the block copolymer can be controlled by adjusting the reaction temperature, the reaction time, the amount of hydrogen supplied, the amount of the catalyst, and the like.

The catalyst to be used in the hydrogenation reaction is not particularly limited. For example, it is known that (1) a carrier such as carbon, cerium oxide, alumina or diatomaceous earth is supported on a metal such as Ni, Pt, Pd or Ru. a supported heterogeneous catalyst; (2) a so-called Ziegler type catalyst using an organic salt such as Ni, Co, Fe, Cr or the like, or a reducing agent such as an ethyl acetonide salt or an organic Al; or an organometallic compound such as Ru or Rh. The so-called organic complex catalyst or the homogeneous catalyst of the organic lithium, organic Al, organic Mg or the like as a reducing agent in the titanocene compound. Among them, from the viewpoints of economy, coloring property of the polymer, or adhesion, it is preferred to use a homogeneous catalyst system in which a lithium ferrocene compound is used as a reducing agent, such as organic Li, organic Al, or organic Mg.

The hydrogenation reaction temperature is preferably from 0 to 200 ° C, more preferably from 30 to 150 ° C. Again, hydrogenation The pressure of hydrogen to be used is preferably 0.1 to 15 MPa, more preferably 0.2 to 10 MPa, still more preferably 0.3 to 5 MPa. Further, the hydrogenation reaction time is preferably from 3 minutes to 10 hours, more preferably from 10 minutes to 5 hours. Further, the hydrogenation reaction may be either a batch process, a continuous process, or a combination of the above.

The hydrogenation method is not particularly limited, and examples thereof include, for example, Japanese Patent Publication No. Sho 42-8704, Japanese Patent Publication No. Sho 43-6636, Japanese Patent Publication No. Sho-63-4841, and Japanese Patent Publication No. Sho 63- The method described in the publication No. 5401.

The hydrogenation reaction is not particularly limited, and from the viewpoint of higher hydrogenation activity, it is preferably carried out after the step of deactivating the active terminal of the polymer described above.

(desolvation step)

The solvent removal step is a step of desolvating a hydrocarbon solvent containing a solution of a polymer. The solvent removal method is not particularly limited, and examples thereof include a method of performing solvent removal by a steam stripping method or a direct solvent removal method. If the steam stripping method is used, it becomes easy to control the specific surface area of the finally obtained crushed material; the cumulative pore volume of the pores having a pore radius of 1 to 100 μm; the average pore radius; the pore radius is 1 μm or more and The maximum value of the log differential pore indentation volume at 100 μm or less is divided by the maximum value of the log differential pore indentation volume when the pore radius is 0.001 μm or more and less than 1 μm ((the pore radius is 1 μm or more and The maximum value of the log differential pore indentation volume at 100 μm or less) / (the maximum value of the log differential pore indentation volume when the pore radius is 0.001 μm or more and less than 1 μm)); and the pore radius is 1~ The cumulative pore volume of the pores of 100 μm is divided by the cumulative pore volume of the pores having a pore radius of 0.001 μm or more and 100 μm (the cumulative pore volume of the pores having a pore radius of 1 μm to 100 μm) / (the cumulative pore volume of the pores having a pore radius of from 0.001 μm to 100 μm) is preferable.

The amount of the residual solvent in the polymer obtained by the method for producing the block copolymer is preferably 2% by mass or less, more preferably 0.5% by mass or less, still more preferably 0.2% by mass or less, and still more preferably 0.05% by mass. The mass% or less is particularly preferably 0.01% by mass or less.

(breaking materialization step)

The aqueous slurry is obtained by dispersing the obtained fracture product of the block copolymer in water by a steam stripping method or the like, and the aqueous slurry is subjected to a dehydration-drying treatment through the following steps, whereby the block can be recovered. The broken product of the copolymer.

As the recovery step of the crushed product of the block copolymer, it is preferred to carry out the following <Step 1> dehydration treatment, <Step 2> dehydration treatment and drying treatment, and <Step 3> drying treatment.

<Step 1>

In the <Step 1>, it is preferred to subject the aqueous slurry obtained by the steam stripping method or the like to a dehydration treatment to obtain a crushed product having a water content of more than 40% by mass and not more than 70% by mass. The water content of the crushed product after <Step 1> is more preferably 42% by mass to 68% by mass, still more preferably 44% by mass to 65% by mass. The dehydration treatment in the <Step 1> can be carried out, for example, by a rotary screen, a vibrating screen, a centrifugal dehydrator or the like. When the water content of the obtained crushed product exceeds 40% by mass, the fluidity of the polymer in the extruder in the following <Step 2> can be suppressed from being lowered, and if the water content is 70% by mass or less, The heat load on the polymer breaker in the extruder in the following step 2 can be suppressed.

<Step 2>

As described above, the crushed material having a specific moisture content by the dehydration treatment in <Step 1> is preferably subjected to dehydration treatment and drying treatment in <Step 2>, and transferred to the following <Step 3>. The water content of the crushed product after the <Step 2> is preferably from 3 to 25% by mass, more preferably from 3 to 20% by mass, still more preferably from 3 to 19% by mass, and still more preferably from 3.2 to 18% by mass. . The dehydration treatment and the drying treatment may be carried out by separate apparatuses, or by a so-called integrated extrusion dryer having a structure in which a dehydration treatment mechanism and a drying treatment mechanism are connected to each other. The extrusion dryer is a device for performing a dehydration treatment and a drying treatment, and includes a dehydration treatment mechanism and a drying treatment mechanism, and as a dehydration treatment mechanism, an extruder (extruder type dehydrator) is used as a drying treatment mechanism. system A kneading type dryer, a spiral type expansion type dryer, or the like is used. From the viewpoint of dehydration efficiency and workability, it is particularly preferable to provide a multi-axis spiral extruder such as a single-shaft or a double-shaft as a dehydration treatment mechanism and a spiral dryer as a drying treatment mechanism. In order to gently control the dewatering of the crushed material, a combination of a single-shaft spiral extruder and a spiral dryer is preferred.

Further, the dewatering apparatus, the drying apparatus, the dehydration processing means, and the drying processing means for performing the <Step 2> are integrated into an extrusion type dryer, specifically, a spiral type extruder, a spiral type dryer, and the like. The body type screw extruder type dryer or the like may be one in which a vent hole mechanism or a dehydration slit is attached depending on the purpose of use.

By the <Step 2>, the water content of the crushed product is 3% by mass or more, whereby the crushed material can be prevented from being gelled and/or decomposed by the shearing force of the extruder, and the moisture content is set. When the amount is 25% by mass or less, the water content of the crushed product obtained by the following <Step 3> can be easily controlled to 1% by mass or less.

In the case of <Step 2>, when the dehydration treatment and the drying treatment are separately performed by the respective devices, it is preferable that the outlet temperature of the apparatus for performing the dehydration treatment is 120 ° C or lower, and the outlet temperature of the apparatus to be subjected to the drying treatment is preferably It is set to 120 ° C or more and less than 175 ° C, and more preferably 120 or more and 170 ° C or less. In the case where the dehydration treatment mechanism and the drying treatment mechanism are integrated into a so-called two-stage extrusion dryer, it is preferable to set the temperature of the first stage outlet to 120 ° C or lower and the second stage. The temperature of the outlet is set to 120 ° C or more and less than 175 ° C, and more preferably 120 ° C or more and 170 ° C or less.

Further, regarding the value of the (production rate) / (opening area of the template) at the outlet of the drying device in <Step 2>, it is preferable to control in a relatively large manner from the viewpoint of the shape of the crushed material, and It is not particularly limited, but is preferably 0.6 (kg/h)/mm ² , more preferably 0.65 (kg/h)/mm ² or more, and still more preferably 0.7 (kg/h)/mm ² or more. The upper limit is not particularly limited, but is preferably 20 (kg/h) / mm ² or less, preferably 10 (kg / h) / mm ² or less.

Here, the production rate at the outlet of the drying device in <Step 2> is the continuous processing amount (kg) after <Step 2> per unit time, and the opening area of the template is included in the mold used. In the case of a single case, the sum of all the opening areas of the mold is also included in the case of a plurality of molds.

The shape of the opening of the mold is not particularly limited, and examples thereof include various shapes in which a plurality of rectangles, triangles, rectangles, and circles are combined, and specific examples thereof include a T-shape and a cross type (cross type). Y-shaped, U-shaped, vertical rectangular, star-shaped, etc.

The shape of the opening of the mold is preferably a diameter of a circle circumscribing the opening of the mold of 0.5 mm or more, and more preferably 1 mm or more. Further, it is preferably 20 mm or less, more preferably 10 mm or less.

<Step 3>

The crushed product obtained in <Step 2> as described above is dried by a hot air dryer in <Step 3> to obtain a crushed product having a water content of 1% by mass or less. The water content of the crushed product after the <Step 3> is preferably 1% by mass or less, more preferably 0.95% by mass or less, still more preferably 0.9% by mass or less. By the <Step 3>, the moisture content of the dried crushed product is 1% by mass or less, thereby having an effect of preventing foaming when the adhesive composition is produced.

Further, the water content of the fracture product of the block copolymer can be determined by the method described in the following examples. It is preferable to adjust the water content of the crushed material after the dehydration treatment of the above <Step 1> so as to be within the above range, and it is more preferable to adjust it within the above range in <Step 1> to <Step 3> The outlet temperature in each device and the moisture content of the fracture at the outlet. By adjusting the water content of the crushed material in each step to the above range, it is possible to obtain a crushed product in which the fluidity of the crushed material is improved and moderately foamed.

About this embodiment the block copolymer morphology of crushed material, a specific surface area of 0.000001m ² / g or more and less than 0.3m ² / g, a pore radius of 1μm ~ 100μm cumulative pore volume of the pores of 0.05mL / g or more and less than 1.0 mL/g, and the average pore radius is 0.00001 μm or more and 1.5 μm or less. Further, (the cumulative pore volume of the pores having a pore radius of from 1 μm to 100 μm) / (the cumulative pore volume of the pores having a pore radius of from 0.001 μm to 100 μm) is preferably from 0.3 to 0.8. In order to obtain such a crushed product, it is particularly effective to adjust the moisture content into the previous stage of <Step 2> and optimize the dehydration-drying conditions in <Step 2>. Specifically, the water content of the crushed product after the <Step 1> is preferably more than 40% by mass and 70% by mass or less as described above, and if the water content is too small, excessive dehydration causes flow in <Step 2>. Reduced sex. On the other hand, if the water content is too large, the dehydration-drying treatment cannot be stably performed in <Step 2>, and good fluidity cannot be obtained. Further, the water content of the crushed material after the dehydration treatment and the drying treatment in <Step 2> is preferably 3% by mass or more and 25% by mass or less, and if the water content of the crushed material is too high, in <Step 3> The load becomes large, and if the water content of the crushed material is too low, the fluidity of the crushed material is lowered and the foaming becomes uneven, so that the desired shape of the crushed material cannot be obtained. Further, in the dehydration treatment and the drying treatment in <Step 2>, it is preferred that the outlet temperature of the apparatus in the dehydration treatment is 120 ° C or lower, and it is preferable to set the outlet temperature of the apparatus in the drying treatment to 120 ° C. Above and less than 175 ° C. When the outlet temperature of <Step 2> is too high, excessive drying occurs, the fluidity of the fractured material is lowered, and the foaming becomes uneven, so that the desired shape of the fractured material cannot be obtained.

Furthermore, the water content of the crushed product after the <Step 1> is set to the above range, and in the dehydration treatment and the drying treatment of <Step 2>, the outlet temperature of the apparatus in the dehydration treatment is set to 120 ° C or less. The outlet temperature of the device in the drying process (in the device integrated with the dehydration treatment mechanism and the drying treatment mechanism, the outlet temperature of the drying treatment mechanism) is controlled to be 120 ° C or more and less than 175 ° C, after <Step 3> The water content of the crushed material is set within the above range, and the (production rate) / (opening area of the template) in <Step 2> is controlled within the above range, whereby the dehydration treatment and the drying treatment can be stably performed, thereby The crushed material having the desired specific surface area, the average pore radius, and the cumulative pore volume of the pores having a pore radius of 1 to 100 μm in the present embodiment can be obtained. A fracture of a block copolymer having excellent adhesion characteristics and an adhesive composition comprising the same.

In order to divide the maximum value of the log differential pores by the pore radius of 1 μm or more and 100 μm or less by the maximum value of the log differential pore indentation volume when the pore radius is 0.001 μm or more and less than 1 μm. Value ((the maximum value of the log differential pore indentation volume when the pore radius is 1 μm to 100 μm) / (the maximum value of the log differential pore indentation volume when the pore radius is 0.001 μm or more and less than 1 μm)) 0.1~2, and the cumulative pore volume is set to 0.0001 mL/g or more and 0.6 mL/g or less, and it is preferable to set the water content of the crushed product after <Step 2> to 3 to 20% by mass, and The temperature of the outlet of the apparatus for drying in <Step 2> or the outlet of the drying treatment means in the apparatus in which the dehydration treatment mechanism and the drying treatment means are integrated is preferably 170 ° C or lower.

From the viewpoint of workability, the crushed product of the block copolymer of the present embodiment is preferably a crushed product having a size of more than 0 μm and not more than 2 μm, and a total amount of crushed material having a size exceeding 5.6 μm. The total amount of the substance is 20% by mass or less. The size of the broken product of the block copolymer can be measured by using an oscillating machine and a plurality of screens. In other words, the screens of the meshes of 6.7 mm, 5.6 mm, 4.0 mm, 3.35 mm, 2.0 mm, and 0.85 mm are superimposed so that the smaller mesh is below, and are placed in the oscillating machine to put the polymer into the net. The largest screen of the eye was oscillated at an oscillation amplitude of 1.5 mm and 3 min, and the amount of broken matter present in each sieve was weighed and calculated.

Further, from the viewpoint of suppressing heat aging resistance or gelation of the fracture product of the block copolymer of the present embodiment, it is preferred to add an antioxidant. The antioxidant is not particularly limited, and examples thereof include a phenol-based antioxidant of a radical scavenger, a phosphorus-based antioxidant of a peroxide decomposer, and a sulfur-based antioxidant. Further, an antioxidant having both properties of a radical scavenger and a peroxide decomposer can be used. These may be used singly or in combination of two or more. Among them, from the viewpoint of suppressing heat aging resistance or gelation of the polymer, it is preferred to add at least a phenol antioxidant.

Further, in terms of color prevention of the polymer or high mechanical strength, a ash removal step of removing the metal in the polymer or a pH adjustment step of the polymer may be performed, for example, adding an acid. Or add carbon dioxide.

The block copolymer constituting the crushed product of the present embodiment which can be produced in the above manner may further comprise: a polar group containing an atom selected from the group consisting of nitrogen, oxygen, helium, phosphorus, sulfur, and tin bonded to the block copolymer The modified polymer of the functional group or the modified block copolymer obtained by modifying the block copolymer with a modifier such as maleic anhydride. Such a modified block copolymer is obtained by subjecting a block copolymer obtained by the above method to a known modification reaction.

The method of imparting such a functional group to the block copolymer is not particularly limited, and examples thereof include a method in which a compound having a functional group is used as a starter, a monomer, a coupling agent or a terminator, and The polymer imparts a functional group.

The initiator containing a functional group, preferably an initiator containing a nitrogen atom, may be exemplified by dioctylamino lithium, di-2-ethylhexylamino lithium, ethylbenzylamino lithium, ( 3-(Dibutylamino)-propyl)lithium, piperidinyllithium, and the like.

Further, examples of the monomer containing a functional group include a compound having a hydroxyl group, an acid anhydride group, an epoxy group, an amine group, a decylamino group, a decyl alcohol group or an alkoxyalkyl group in the monomer used in the polymerization. Among them, a monomer having a group having a nitrogen atom is preferred, and is not particularly limited, and examples thereof include N,N-dimethylvinylbenzylamine, N,N-diethylvinylbenzylamine, and N. N-dipropylvinylbenzylamine, N,N-dibutylvinylbenzylamine, N,N-diphenylvinylbenzylamine, 2-dimethylaminoethylstyrene, 2-diethyl Aminoethylstyrene, 2-bis(trimethyldecyl)aminoethylstyrene, 1-(4-N,N-dimethylaminophenyl)-1-phenylstyrene, N,N-Dimethyl-2-(4-vinylbenzyloxy)ethylamine, 4-(2-pyrrolidinyl)styrene, 4-(2-piperidinylethyl)styrene 4-(2-hexamethyleneiminoethyl)styrene, 4-(2- Lolinylethyl)styrene, 4-(2-thiazinoethyl)styrene, 4-(2-N-methylpiperazinylethyl)styrene, 1-((4-vinylphenoxy) Methyl)pyrrolidine, 1-(4-vinylbenzyloxymethyl)pyrrolidine, and the like.

Further, examples of the coupling agent and the terminating agent containing a functional group include a compound containing a hydroxyl group, an acid anhydride group, an epoxy group, an amine group, a decylamino group, a decyl alcohol group, or an alkoxyalkyl group in the above coupling agent. Among them, a coupling agent containing a group containing a nitrogen atom or a group containing an oxygen atom is preferred, and is not particularly limited, and examples thereof include tetraglycidyl meta-xylene diamine and tetraglycidyl-1,3-double. Aminomethylcyclohexane, tetraglycidyl-p-phenylenediamine, tetraglycidyldiaminodiphenylmethane, diglycidylaniline, γ-caprolactone, γ-glycidyloxy Ethyltrimethoxydecane, γ-glycidoxypropyltrimethoxydecane, γ-glycidoxypropyltriphenoxydecane, γ-glycidoxypropylmethyldimethoxydecane, Γ-glycidoxypropyl diethyl ethoxy decane, 1,3-dimethyl-2-imidazolidinone, 1,3-diethyl-2-imidazolidinone, N, N'-di Methyl propyl urea, N-methyl pyrrolidone, and the like.

[Adhesive composition]

The adhesive composition of the present embodiment contains 100 parts by mass of the polymer including the crushed product of the above block copolymer, 20 to 500 parts by mass of the adhesion-imparting agent, and 0 to 300 parts by mass of the softening agent. The adhesive composition of the present embodiment has excellent adhesion, viscosity, and holding power, and has excellent adhesion properties, low viscosity characteristics, and texture, and is excellent in balance.

Further, the adhesive composition contains a styrene-butadiene block copolymer, a styrene-isoprene block copolymer, and a hydrogenation other than the block copolymer constituting the crushed product of the present embodiment. Styrene-butadiene block copolymer, hydrogenated styrene-isoprene block copolymer, styrene-butadiene-isoprene block copolymer, hydrogenated styrene-butadiene In the case of an isoprene-based block copolymer or the like, the content of the block copolymer other than the present embodiment and the block copolymer crushed product of the present embodiment is 100 parts by mass, and the following 20 to 500 parts by mass of the adhesion-imparting agent and 0 to 300 parts by mass of the softening agent described below.

Furthermore, it is preferred to select a block copolymer, such as a block copolymer, depending on the application. The weight average molecular weight of the components (A) and (B), and the blending amount of each component such as an adhesion-imparting agent and a softener.

(adhesive agent)

The adhesion-imparting agent can be variously selected depending on the use and required properties of the obtained adhesive composition. In the present specification, the adhesion-imparting agent is not a polymer which does not belong to the fractured product of the block copolymer of the present embodiment. The adhesive agent is not particularly limited, and examples thereof include natural rosin, modified rosin, glycerin of natural rosin, glycerin of modified rosin, pentaerythritol ester of natural rosin, pentaerythritol ester of modified rosin, hydrogenated rosin, and hydrogenation. a rosin-based compound such as pentaerythritol ester of rosin; a copolymer of natural terpene, a three-dimensional polymer of natural terpene, an aromatic modified terpene resin, a hydrogenated derivative of an aromatic modified terpene resin, a terpene phenol resin, and an anthracene Hydrogenated derivatives of phenolic resins, terpene resins (monoterpene, diterpene, triterpene, polydecene, etc.), terpene compounds such as hydrogenated terpene resins; aliphatic petroleum hydrocarbon resins (C5 based resins) Hydrogenated derivative of aliphatic petroleum hydrocarbon resin, aromatic petroleum hydrocarbon resin (C9 resin), hydrogenated derivative of aromatic petroleum hydrocarbon resin, dicyclopentadiene resin, and hydrogenation of dicyclopentadiene resin A petroleum hydrocarbon compound such as a C5/C9 copolymerization resin, a hydrogenated derivative of a C5/C9 copolymerization resin, a cyclic aliphatic petroleum hydrocarbon resin, or a hydrogenated derivative of a cyclic aliphatic petroleum hydrocarbon resin. These adhesion-imparting agents may be used alone or in combination of two or more.

As the adhesive-imparting agent, a liquid-type adhesive which imparts a colorless color to a pale yellow color and which has substantially no odor and is excellent in thermal stability can be used.

Hereinafter, a preferred adhesion-imparting agent for use and performance will be described more specifically.

(adhesive imparting agent for hydrogenated derivatives)

The adhesion-imparting resin is preferably a hydrogenated derivative from the viewpoint of the difficulty of coloring or the level of odor. The hydrogenated derivative is not particularly limited, and examples thereof include a hydrogenated derivative of an aromatic modified terpene resin, a hydrogenated derivative of a terpene phenol resin, and an aliphatic petroleum. Hydrogenated derivative of hydrocarbon resin (C5 resin), hydrogenated derivative of aromatic petroleum hydrocarbon resin (C9 resin), hydrogenated derivative of dicyclopentadiene resin, hydrogenated derivative of C5/C9 copolymerized resin A hydrogenated derivative of a cyclic aliphatic petroleum hydrocarbon resin. Among them, a hydrogenated derivative of an aromatic petroleum hydrocarbon resin (C9 resin), a hydrogenated derivative of a dicyclopentadiene resin, and the like are preferable. The commercial product of such a hydrogenated derivative is not particularly limited, and examples thereof include Arkon P90, Arkon P100, Arkon P115, Arkon P125, Arkon P140 (trade name), Arkon M90, Arkon M100, and Arkon manufactured by Arakawa Chemical Co., Ltd. M115, Arkon M135 (trade name), Ester gum H, Ester gum HP (trade name), HYPALE (trade name); Regalite R1010 manufactured by Eastman Chemical Co., Regalite R1090, Regalite R1100, Regalite S5100, Regalite R7100, Regalite C6100 ( Product name), East Tack C100W, East Tack C100L, East Tack C100R, East Tack C115W, East Tack C115R (trade name), Staybelite E (trade name), FORAL AXE (trade name), Staybelite ester 10E (trade name); Clearon P (trade name), Clearon M (trade name), Clearon K (trade name), YS Polyster UH (trade name) manufactured by Yasuhara Chemical Co., Ltd.; Escorez 5340, Escorez 5320, Escorez 5300, Escorez 5380 manufactured by Exxon Co., Ltd. Escorez 5400, Escorez 227E, Escorez 5600, Escorez 5690 (trade name); Quintone A100, Quintone B170, Quintone M100, Quintone R100, Quin, manufactured by ZEON Corporation, Japan Tone S195, Quintone D100, Quintone U185, Quintone DX395, Quintone 390N, Quintone N180, Quintone G100B, Quintone G115, Quintone E200SN, Quintone D200, Quintone 1105, Quintone 1325, Quintone 1340 (trade name); I manufactured by Idemitsu Kosan Co., Ltd. -MARV S100, I-MARV S110, I-MARV P100, I-MARV P125, I-MARV P140 (trade name); Rika Rosin F (trade name) manufactured by Rika Finetech Co., Ltd., and the like. (adhesive imparting agent other than hydrogenated derivatives)

The adhesion-imparting agent other than the hydrogenated derivative is not particularly limited, and for example, it can be listed. Lift: natural rosin, modified rosin, glycerin of natural rosin, glycerin of modified rosin, pentaerythritol ester of natural rosin, pentaerythritol ester of modified rosin; copolymer of natural terpene, three-dimensional polymer of natural terpene, Aromatic modified terpene resin, terpene phenol resin, terpene resin; aliphatic petroleum hydrocarbon resin (C5 resin), aromatic petroleum hydrocarbon resin (C9 resin), dicyclopentadiene resin, C5/C9 A copolymer resin or a cyclic aliphatic petroleum hydrocarbon resin. Among them, aliphatic petroleum hydrocarbon resin (C5 system), aromatic petroleum hydrocarbon resin (C9 resin), C5/C9 copolymer resin, cyclic aliphatic petroleum hydrocarbon resin, terpene resin, natural and modified are preferred. Rosin esters, and mixtures of these. As a commercial item, Ester gum AA-L, Ester gum A, Ester gum AAV, Ester gum, Ester gum 105, Ester gum AT, Pencel A, Pencel AZ, Pencel C, Pencel D125 manufactured by Arakawa Chemical Co., Ltd. Pensel D160 (trade name), Super ester (trade name), TAMANOL (trade name), PINECRYSTAL (trade name), ARADIME (trade name); Wingtack10, Wingtack95, Wingtack98, Wingtack Extra, Wingtack RWT-7850 manufactured by CrayValley, Wingtack PLUS, Wingtack ET, Wingtack STS, Wingtack 86 (trade name), Norsolnene (product name); Piccotac 8095, Piccotac 1095, Piccotac 1098, Piccotac 1100 (trade name) manufactured by Eastman Chemical Co., Ltd.; Escorez 1102, Escorez 1202, Escorez manufactured by ExxonMobil Chemical Co., Ltd. 1204LS, Escorez 1304, Escorez 1310, Escorez 1315, Escorez 224, Escorez 2101, Escorez 213, Escorez 807 (trade name); Sylvagum (trade name) and Sylvalite (trade name) manufactured by ARIZONA Chemical Co., Ltd.; and Piccolyte (made by Ashland) Product name); YS Resin PX (trade name) and YS Resin PXN (trade name) manufactured by Yasuhara Chemical Co., Ltd. YS Polyster U (trade name), YS Polyster T (product name), YS Polyster S (product name), YS Polyster G (product name), YS Polyster N (trade name), YS Polyster K (trade name), YS Polyster TH (trade name), YS Resin TO (trade name), YS Resin TR (trade name), YS Resin SX (trade name); Maruzen Petrochemical MARUKAREZ M (trade name) manufactured by the company.

(aliphatic adhesion-imparting agent)

From the viewpoint of obtaining an adhesive composition having high adhesiveness, high retention, and economy, it is preferred to use an aliphatic adhesion-imparting agent as an adhesion-imparting agent. The aliphatic-based adhesion-imparting agent is not particularly limited, and examples thereof include an aliphatic petroleum hydrocarbon resin (C5 resin), a hydrogenated derivative of an aliphatic petroleum hydrocarbon resin (C5 resin), and a C5/C9 copolymer resin. a hydrogenated derivative of a C5/C9 copolymerization resin, a cyclic aliphatic petroleum hydrocarbon resin, or a hydrogenated derivative of a cyclic aliphatic petroleum hydrocarbon resin. In addition, the aliphatic-based adhesion-imparting agent means that the content of the aliphatic hydrocarbon group is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 80% by mass or more, and still more preferably 88% by mass. More preferably, it is more preferably 95% by mass or more of the adhesion-imparting agent. When the content of the aliphatic hydrocarbon group is within the above range, the adhesiveness, retention, and economy tend to be improved.

The aliphatic adhesion-imparting agent can be produced by homopolymerizing or copolymerizing a monomer having an aliphatic group and a polymerizable unsaturated group. The monomer having an aliphatic group and a polymerizable unsaturated group is not particularly limited, and examples thereof include natural and synthetic terpenes containing a C5 or C6 cyclopentyl group or a cyclohexyl group. Further, the other monomer which can be used in the copolymerization is not particularly limited, and examples thereof include 1,3-butadiene, cis-1,3-pentadiene, and trans-1,3-pentane. Diene, 2-methyl-1,3-butadiene, 2-methyl-2-butene, cyclopentadiene, dicyclopentadiene, decene, terpene-phenol resin, and the like.

(Aromatic adhesion promoter)

From the viewpoint of obtaining an adhesive composition having high adhesion and high coatability, it is preferred to use an aromatic adhesion-imparting agent as an adhesion-imparting agent. The aromatic-based adhesion-imparting agent is not particularly limited, and examples thereof include an aromatic petroleum hydrocarbon resin (C9-based resin) and a C5/C9 copolymer-based resin. In addition, the aromatic-based adhesion-imparting agent means that the content of the aromatic hydrocarbon group is preferably 50% by mass or more, and more preferably 70% by mass. The above is more preferably 80% by mass or more, still more preferably 88% by mass or more, and still more preferably 95% by mass or more of the adhesion-imparting agent. When the content of the aromatic hydrocarbon group is within the above range, the adhesion and the coating property tend to be improved.

The aromatic-based adhesion-imparting agent can be produced by homopolymerizing or copolymerizing monomers each having an aromatic group and a polymerizable unsaturated group. The monomer having an aromatic group and a polymerizable unsaturated group is not particularly limited, and examples thereof include styrene, A-methylstyrene, vinyltoluene, methoxystyrene, and tert-butyl group. Styrene, chlorostyrene, fluorene monomer (including methyl hydrazine). Further, the other monomer which can be used in the copolymerization is not particularly limited, and examples thereof include 1,3-butadiene, cis-1,3-pentadiene, and trans-1,3-pentane. Diene, 2-methyl-1,3-butadiene, 2-methyl-2-butene, cyclopentadiene, dicyclopentadiene, decene, terpene-phenol resin, and the like. Commercial products include ENDEX 155 (trade name) manufactured by Eastman Chemical Co., Ltd., Crystalex 1120, Crystalex 3085, Crystalex 3100, Crystalex 5140, Crystalex F100 (trade name), PLASTOLYN 240, PLASTOLYN 290, PICOTEX 100 (trade name), and the like. (Adhesive imparting agent having affinity for the glass phase of the block copolymer (for example, polymer block (Ar)) and/or non-glass phase (for example, polymer block (D)))

As the adhesive composition, high adhesion, subsequent strength change or creep property (good value is small), low melt viscosity, heat resistance, etc. or a good balance of these In view of the above, it is preferred that the adhesive agent of the non-glass phase block (usually a mid-block) containing the block copolymer in the adhesive composition has an affinity of 20 to 75% by mass, and the block is The block of the glass phase of the copolymer (usually the outer block) has an affinity adhesion-imparting agent of 0.1 to 30% by mass. Here, as the block copolymer, it is preferred to include the above components (A) and (B).

The adhesion-imparting agent having an affinity for a block of the non-glass phase of the block copolymer (for example, the polymer block (D)) is not particularly limited, and examples thereof include a rosin-based compound and a terpene-based compound. Aliphatic petroleum hydrocarbon resin (C5 resin), aliphatic petroleum hydrocarbon resin Hydrogenated derivative, C5/C9 copolymerized resin, hydrogenated derivative of C5/C9 copolymerized resin, cyclic aliphatic petroleum hydrocarbon resin, hydrogenated derivative of cyclic aliphatic petroleum hydrocarbon resin, and the like. The content of the adhesion-imparting agent having an affinity for the non-glass phase of the block copolymer is preferably from 20 to 75% by mass, more preferably from 25 to 70% by mass, based on 100% by mass of the adhesive composition. It is preferably 30 to 65 mass%.

The adhesion-imparting agent having an affinity for the block of the glass phase of the block copolymer (for example, the polymer block (Ar)) is not particularly limited, and for example, a resin having an aromatic ring in the molecule is preferable. The resin is not particularly limited, and examples thereof include aromatic groups such as a homopolymer or a copolymer containing vinyl toluene, styrene, α-methylstyrene, smoked mash, or hydrazine as a structural unit. Resin. Further, among these, Kristalex or Plascolyn and Piccotex (trade name, manufactured by Eastman Chemical Co., Ltd.) having α-methylstyrene are preferred.

The content of the adhesion-imparting agent having an affinity for the block of the glass phase of the block copolymer is preferably from 0.5 to 30% by mass, more preferably from 1 to 20% by mass, based on 100% by mass of the adhesive composition. Further, it is preferably 2 to 12% by mass.

For the purpose of higher initial adhesion, higher wettability, lower melt viscosity of the adhesive composition, or higher coatability, it is preferred to use aroma content of 3 to 12 The mass% of petroleum resin is used as an adhesion-imparting agent. The petroleum resin is not particularly limited, and examples thereof include an aliphatic petroleum hydrocarbon resin (C5 resin), a hydrogenated derivative of an aliphatic petroleum hydrocarbon resin (C5 resin), and an aromatic petroleum hydrocarbon resin (C9 resin). ), a hydrogenated derivative of an aromatic petroleum hydrocarbon resin (C9 resin), a dicyclopentadiene resin, a hydrogenated derivative of a dicyclopentadiene resin, a C5/C9 copolymer resin, and a C5/C9 copolymerization A hydrogenated derivative of a resin, a cyclic aliphatic petroleum hydrocarbon resin, or a hydrogenated derivative of a cyclic aliphatic petroleum hydrocarbon resin. The aroma content of the petroleum resin is preferably from 3 to 12% by mass, more preferably from 4 to 10% by mass. Among them, it is especially preferred to be a hydrogenated petroleum resin.

Also, it is necessary to have higher weather resistance (lower adhesion change after UV irradiation) In the case of the shape, the adhesion-imparting agent is preferably a hydrogenated adhesion-imparting resin. The "hydrogenated adhesion-imparting resin" refers to an adhesion-imparting resin obtained by hydrogenating an aliphatic-based adhesion-imparting resin containing an unsaturated bond or an aromatic-based adhesion-providing resin containing an unsaturated bond to have an arbitrary hydrogenation ratio. . It is preferred that the hydrogenation rate is higher.

From the viewpoints of higher initial adhesion, higher wettability, lower melt viscosity of the adhesive composition, or higher coatability, it is preferred to use styrene oligomer as adhesion. Agent. The styrene oligomer is not particularly limited, and examples thereof include an aromatic petroleum hydrocarbon resin (C9-based resin) such as Piccolastic A5 (trade name) or Piccolastic A75 (trade name, manufactured by Eastman Chemical Co., Ltd.).

The content of the styrene oligomer is preferably 35% by mass or less, more preferably 30% by mass or less, and still more preferably 25% by mass or less based on 100% by mass of the adhesive composition.

From the viewpoints of very low odor, high weather resistance, high transparency, colorlessness, and low heat discoloration, it is preferred to use a hydrogenated resin (for example, the above hydrogenated derivative) as an adhesive bond. Agent.

The content of the adhesion-imparting agent is 20 parts by mass or more, preferably 30 parts by mass or more, more preferably 50 parts by mass or more, and further preferably 50 parts by mass or more based on 100 parts by mass of the polymer containing the crushed product of the block copolymer. 75 parts by mass or more. In addition, the content of the adhesion-imparting agent is 500 parts by mass or less, preferably 400 parts by mass or less, and more preferably 350 parts by mass or less based on 100 parts by mass of the crushed product of the block copolymer. In addition, the content of the adhesion-imparting agent is 20 to 500 parts by mass, preferably 30 to 400 parts by mass, more preferably 50 to 350 parts by mass, even more preferably 100 parts by mass of the crushed product of the block copolymer. It is 75 to 350 parts by mass. The content of the adhesion-imparting agent is within the above range, and the adhesion property is further improved.

Further, in the case where the adhesive composition of the present embodiment contains the crushed product of the block copolymer of the present embodiment and other polymers, the content of the adhesion-imparting agent is block copolymerization with respect to the present embodiment. The total amount of broken matter and other polymers The mass portion is 20 to 500 parts by mass, preferably 30 to 400 parts by mass, more preferably 50 to 350 parts by mass, still more preferably 75 to 350 parts by mass. The content of the adhesion-imparting agent is within the above range, and the adhesion property is further improved.

(softener)

The term "softener" means a function of lowering the hardness of the adhesive composition and lowering the viscosity. Further, in the present specification, the softener is a polymer which does not belong to the crushed product including the block copolymer of the present embodiment. The softening agent is not particularly limited, and examples thereof include petroleum-based oils such as a known paraffin-based processing oil, a naphthenic processing oil, an aromatic processing oil, an extender oil, and the like; Sex oil; plasticizer; synthetic liquid oligomer; and mixtures of such.

The following, for the purpose of use. A preferred softener of performance is more specifically described.

As the softening agent, the viscosity of the adhesive composition is lowered, the adhesiveness is improved, and the hardness is lowered. The oil is not particularly limited, and examples thereof include a known paraffin-based processing oil, a naphthenic processing oil, an aromatic processing oil, an extender oil, and the like. From the viewpoint of weather resistance, low odor characteristics, low-temperature characteristics, aging resistance, stain resistance, and color tone, a paraffin-based processing oil is preferred, and from the viewpoint of compatibility, aromatic processing is preferred. The oil is preferably a naphthenic processing oil from the viewpoint of balance between economy, low-temperature characteristics, aging resistance, stain resistance, color tone, and compatibility.

When the adhesive composition is used as a percutaneous absorption preparation, a plasticizer can be used as a viewpoint of improving transdermal absorbability and storage stability and improving drug solubility in the adhesive composition. Softener. The plasticizer is not particularly limited, and examples thereof include liquid paraffin, isopropyl myristate, ethyl laurate, and isopropyl palmitate, and a higher fatty acid having a carbon number of 12 to 16 and a carbon number of 1 to 4. Fatty acid ester of low carbon monohydric alcohol; fatty acid having 8-8 carbon atoms; ethylene glycol, diethylene glycol, triethylene glycol, polyethylene Alcohol, propylene glycol, polypropylene glycol and other alcohols; olive oil, castor oil, squalene, lanolin and other oils; ethyl acetate, ethyl alcohol, dimethyl hydrazide, fluorenylmethyl hydrazine, two Organic solvent such as methyl hydrazine, dimethylformamide, dimethylacetamide, dimethyl lauryl decylamine, dodecyl pyrrolidone, isosorbide, oleyl alcohol, lauric acid; liquid Surfactant; ethoxylated stearyl alcohol, glyceryl ester, isotridecyl myristate, N-methylpyrrolidone, ethyl oleate, oleic acid, diisopropyl adipate, palmitic acid octyl Ester, 1,3-propanediol, glycerin, and the like. Among these, a compound which is liquid at normal temperature is used. Among them, a glyceride is preferable, and a long-chain triglyceride which is an ester of a fatty acid having 8 to 10 carbon atoms and glycerin is more preferable. Examples of the medium long chain triglyceride include tris(octanoic acid/capric acid) glyceride. The plasticizer may be used alone or in combination of two or more.

In the case where an adhesive composition and a tape are used as a medical tape such as a wrapping tape, it is preferred to use a liquid paraffin in combination with other plasticizers as a softening agent.

The plasticizer is not particularly limited, and examples thereof include a dibasic acid ester such as DBP (dibutyl phthalate) or DOP (Dioctyl Phthalate).

When the adhesive composition and the adhesive tape are used for medical use, the amount of the liquid plasticizer added is preferably from 3 to 30% by mass, more preferably from 3 to 30% by mass, based on 100% by mass of the adhesive composition. 3 to 20% by mass, and more preferably 3 to 10% by mass. When the amount of the liquid plasticizer added is 3% by mass or more, there is a tendency that the transdermal absorbability, storage stability, and drug solubility in the adhesive composition are further improved. In addition, when the amount of the liquid plasticizer added is 30% by mass or less, the cohesive force of the adhesive composition tends to be further improved.

In the case where the adhesive composition is to be made softer, a synthetic liquid oligomer can be used from the viewpoint of improvement in exudation property. The synthetic liquid oligomer is not particularly limited as long as it is called a liquid rubber, and examples thereof include a styrene oligomer, a butadiene oligomer, an isoprene oligomer, and a butene oligomerization. Materials, isobutylene oligomers, and the like.

In the case where a component derived from nature is used as a softening agent, a vegetable oil is preferred. The vegetable oil is not particularly limited, and examples thereof include castor oil, tall oil, and turpentine. From the viewpoint of cold resistance, castor oil is preferred.

The commercial product of such a softening agent is not particularly limited, and examples thereof include Diana Fresia S32, Diana Process Oil PW-32, PW-90, PW-150, PS-430, and Diana Process manufactured by Idemitsu Kosan Co., Ltd. Oil NP-24, NR-26, NR-68, NS-90S, NS-100, NM-280, Diana Process Oil AC-12, AC-640, AH-16, AH-24, AH-58 (trade name) ); White Oil Broom 350 (trade name) manufactured by Kukdong Oil & Chem Co., Ltd., DN oil KP-68 (trade name); Enerper M1930 (trade name) manufactured by BP Chemicals; Kaydol (trade name) manufactured by Crompton; Exxon Manufactured by Primol 352 (trade name); KN4010 (trade name) manufactured by PetroChina Company; Syntac N-40, N-60, N-70, N-75, N-80, Syntac PA-95, manufactured by Kobe Oil Chemicals, PA-100, PA-140, Syntac HA-10, HA-15, HA-30, HA-35 (trade name); JOMO Process P200, P300, P500, 750, JOMO Process R25, R50, R200 manufactured by Japan Energy , R1000, JOMO Process X50, X100E, X140 (trade name); SUNPAR 110, 115, 120, 130, 150, 2100, 2280, Sunthene Oil 310, 410, 415, 420 manufactured by Japan Sun Oil, 430, 450, 380, 480, 3125, 4130, 4240, JSO Aroma 790, Neoprene 720L (trade name); Furoeckol process P-100, P-200, P-300, P-400, P- 500, Furoeckol New flex 1060W, 1060E, 1150W, 1150E, 1400W, 1400E, 2040E, 2050N, Furoeckol Aromax 1, 3, 5, EXP1 (trade name); Shell flex 371JY (trade name) manufactured by Shell Japan; Petrochemical process oil PN-3, PN-3M, PN-3N-H (trade name), Petrex process oil LPO-R, LPO-V, PF-2 (trade name); Cosmo made by Cosmo Oil Lubricants Process 40, 40A, 40C, 200A, 100, 1000 (trade name), etc.

The content of the softening agent in the adhesive composition of the present embodiment is 0 to 300 parts by mass, preferably 10 to 175 parts by mass, more preferably 20 to 150 parts by mass based on 100 parts by mass of the block copolymer composition. Parts by mass. When the content of the softener is within the above range, the adhesive property is further improved.

Further, the content of the softening agent is preferably 35% by mass or less, more preferably 3% by mass or more and 30% by mass or less based on 100% by mass based on the total mass of the adhesive composition. When the content of the softener is within the above range, the adhesive property is further improved.

Further, in the case where the adhesive composition of the present embodiment contains the crushed product of the block copolymer of the present embodiment and other polymers, the content of the softener is compared with the block copolymer of the present embodiment. The total amount of the crushed material and the other polymer is from 0 to 300 parts by mass, preferably from 10 to 175 parts by mass, more preferably from 20 to 150 parts by mass. When the content of the softener is within the above range, the adhesive property is further improved.

(other ingredients)

The adhesive composition of the present embodiment may contain a crushed product of the above block copolymer as needed (including a specific monomer unit, a weight average molecular weight of 20,000 to 1,000,000, and satisfying the necessary conditions (a), (b) And other polymers, waxes, polar group-containing polymers, stabilizers, and fine particle fillers, antistatic agents, lubricating materials, and the like, other than the crushed product of the block copolymer block of (c).

(other polymers)

The other polymer is not particularly limited, and examples thereof include a polyolefin-based copolymer, a vinyl aromatic elastomer, and other rubbers. In the present specification, the term "other polymer" means that the weight average molecular weight which is not described as the block copolymer of the present embodiment is 20,000 to 1,000,000, and the necessary conditions (a) and (() are satisfied. The polymer of the fracture of the block copolymer block of b), and (c).

The polyolefin or the polyolefin-based copolymer is not particularly limited, and examples thereof include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, and 1 - Xin A polymer of one or two or more kinds of monomers such as an alkene or a 1-decene, or a random polypropylene or an ethylene-ethyl acrylate copolymer. As a commercial product of polyolefin, VESTOPLAST 408, VESTOPLAST 508, VESTOPLAST 703, VESTOPLAST 704, VESTOPLAST 708 (trade name) manufactured by Degussa Co., Ltd.; Licocene PP1302, Licocene PP1502, Licocene PP 1602, and Licocene PP2602 manufactured by Clariant Japan Co., Ltd. (trade name), etc.

The vinyl aromatic elastomer is not particularly limited, and examples thereof include a styrene-ethylene block copolymer, a styrene-butadiene block copolymer, and a styrene-propylene block copolymer. Styrene-isoprene block copolymer, styrene-butadiene-isoprene block copolymer, hydrogenated styrene-butadiene block copolymer, hydrogenated styrene-isoprene The olefin-based block copolymer, the hydrogenated styrene-butadiene-isoprene-based block copolymer, or the like, which is a polymer other than the polymer constituting the crushed product of the block copolymer of the present embodiment.

As a commercial item of the styrene-isoprene block copolymer, Quintac 3421, Quintac 3620, Quintac 3433N, Quintac 3520, Quintac 3450, Quintac 3270, Quintac 3280, Quintac 3390 (made by Japan ZEON Co., Ltd.) are mentioned. Trade name); D1107P, D1111, D1112P, D1113P, D1114PX, D1117P, D1119P, D1124P, D1128PX, D1193P, D4433P (trade name) manufactured by Kraton Polymers, Inc.; Vector 4111A, Vector 4111N, Vector 4113A, Vector 4113N, manufactured by TSRC , Vector 4114A, Vector 4114N, Vector 4186A, Vector 4187A, Vector 4211A, Vector 4211N, Vector 4213A, Vector 4213N, Vector 4215A, Vector 4230, Vector 4293A, Vector 4411A (trade name), as styrene-butadiene Commercial products of the segment copolymers include D1101, D1102, D1116, D1118, D1122, D1133, D1144, D1184, D4141, D4150, and D4158 (trade names) manufactured by Kraton Polymers, Inc.; Vector 2336, Vector manufactured by TSRC Corporation. 2411, Vector 2411P, Vector 2518, Vector 2518A, Vector 2518LD, Vector 2518P, Vector 2518PC, Vector, Vector 6241A, Vector 7400, Vector 8508, Vector 8508A, Tiepolo 3201, Tiepolo 3206, Tiepolo 4202, Tiepolo 4230, Tiepolo 4270 (trade name); Tufprene A, Tufprene 125, manufactured by Asahi Kasei Chemicals Co., Ltd. Tufprene 126S, Tufprene 315P, Asaprene T411, Asaprene T412, Asaprene T413, Asaprene T420, Asaprene T432, Asaprene T436, Asaprene T437, Asaprene T438, Asaprene T439 (trade name) and the like. Examples of commercially available hydrogenated styrene-isoprene block copolymers include G1701, G1702, G1750X, G1765X, and G1780X (trade names) manufactured by Kraton Polymers, Inc.; Septon 1001, Septon 1020, and Septon 2002 manufactured by Kuraray Co., Ltd. , Septon 2004, Septon 2005, Septon 2006, Septon 2007, Septon 2063, Septon 2104 (trade name), and the like. Examples of commercially available hydrogenated styrene-butadiene block copolymers include G1643, G1645, G1650, G1651, G1652, G1654, G1657, and G1726 (trade names) manufactured by Kraton Polymers, Inc.; Septon 8004, Septon 8006, Septon 8007, Septon 8076, Septon 8104 (trade name); Tiepolo 6150, Tiepolo 6151, Tiepolo 6152, Tiepolo 6154, Tiepolo 6159 (trade name) manufactured by TSRC Corporation; H1221, H1062, H1052, H1041 manufactured by Asahi Kasei Chemicals Co., Ltd. H1051, H1057, H1043, N504 (trade name), and the like. Examples of the commercially available hydrogenated styrene-butadiene-isoprene block copolymer include Septon 4033, Septon 4044, Septon 4055, Septon 4077, and Septon 4099 (trade name) manufactured by Kuraray Co., Ltd., and the like.

In addition, the content of the vinyl aromatic elastomer which is another polymer in the adhesive composition is preferably 100 parts by mass based on 100 parts by mass of the total of the crushed product of the block copolymer of the present embodiment and other polymers. 0 to 95 parts by mass, more preferably 5 to 95 parts by mass, still more preferably 10 to 90 parts by mass, and still more preferably 15 to 85 parts by mass.

Other rubbers are not particularly limited, and examples thereof include natural rubber and isoprene. Diene-isobutylene rubber, polyisoprene rubber, polybutadiene rubber, styrene-butadiene rubber, styrene-isoprene rubber, propylene-butene rubber, ethylene-propylene rubber, chloroprene Synthetic rubber such as olefin rubber, acrylic rubber, or polypentene rubber. Among them, natural rubber is preferred from the viewpoint of crosslinkability or economy.

By using natural rubber, the cross-linking property of the adhesive composition is further improved, and the economy is also excellent.

The content of the natural rubber is preferably 0 to 90 parts by mass, more preferably 3 to 90% by mass, still more preferably 10 to 80% by mass, and still more preferably 15% by mass based on 100% by mass of the adhesive composition. ~75% by mass. When the content of the natural rubber is within the above range, the crosslinkability, heat resistance, solvent resistance, and economy of the adhesive composition tend to be improved.

Hereinafter, other polymers depending on the use and performance will be more specifically described.

(hydrogenated vinyl aromatic elastomer)

The adhesive is attached to the adherend, and the residue of the adhesive is removed, and the change in the strength of the subsequent strength is suppressed or creeped (the value is smaller), heat resistance, weather resistance, and the like. In other words, a hydrogenated vinyl aromatic elastomer can be used. The hydrogenated vinyl aromatic elastomer is not particularly limited, and examples thereof include hydrogenated benzene having a structure such as S-EB-S (S: polystyrene block, EB: ethylene/butylene copolymer block). An ethylene-butadiene-based block copolymer; a hydrogenated styrene-isoprene block having a structure such as S-EP-S (S: polystyrene block, EP: ethylene/propylene copolymer block) Copolymer; hydrogenated styrene-butadiene-isoprene block copolymer having the structure of S-EEP-S (S: polystyrene block, EEP: ethylene/ethylene/propylene copolymer block) Wait. Among them, a hydrogenated styrene-butadiene block copolymer or a hydrogenated styrene-isoprene block copolymer is preferred.

The styrene content of the hydrogenated vinyl aromatic elastomer is preferably 10% by mass to 45% by mass, and more preferably 13% by mass to 40% by mass based on 100% by mass of the hydrogenated vinyl aromatic elastomer. Further, it is preferably 15% by mass to 35% by mass.

In addition, the content of the polystyrene block of the hydrogenated vinyl aromatic elastomer is preferably 30% by mass or less, and more preferably 21% by mass or less based on 100% by mass of the hydrogenated vinyl aromatic elastomer. Further, it is preferably 15% by mass or less. When the content of the polystyrene block is within the above range, the flexibility or compatibility tends to be further improved.

Further, the content of B (butene monomer unit) in the ethylene/butene copolymer block in the hydrogenated vinyl aromatic elastomer is preferably as high as possible, and is relative to the hydrogenated vinyl aromatic elastomer. The monomer unit is 100 mol%, preferably 35 mol% or more, more preferably 45 mol% or more, further preferably 55 mol% or more, and particularly preferably 60 mol% or more. When the content of B in the ethylene/butene copolymer block is within the above range, flexibility or compatibility tends to be further improved.

Further, the hydrogenation ratio of the unsaturated group in the monomer unit of the conjugated diene compound in the hydrogenated vinyl aromatic elastomer is preferably more than 80 mol%.

(non-hydrogenated vinyl aromatic elastomer)

As the adhesive composition, the adhesive composition may also contain a non-hydrogenated vinyl aromatic compound from the viewpoints of higher flexibility, higher adhesion, inhibition of gelation, or higher economic efficiency. Elastomers. The non-hydrogenated vinyl aromatic elastomer is not particularly limited, and examples thereof include a styrene-ethylene block copolymer, and SBS and (SB) _n X (S: polystyrene block, B: poly a styrene-butadiene block copolymer having a structure such as a butadiene block, X: a residue of a coupling agent; a styrene-propylene block copolymer; having SIS, (SI) _n X (S: a styrene-isoprene block copolymer having a structure of polystyrene block, I: polyisoprene block, X: a residue of a coupling agent; having (S-(I/B)) _n X, S-(I/B)-S (S: polystyrene block, I/B: isoprene/butadiene copolymer block (isoprene and butadiene can also be used arbitrarily A styrene-butadiene-isoprene block copolymer having a structure in which the ratios are alternately arranged, and the above ratio may not be fixed), X: a residue of a coupling agent. Among them, (SI) _n X, (SB) _n X, (S-(I/B)) _n X is preferable, and a star structure is more preferable. These may be used alone or in combination of two or more.

The styrene content of the non-hydrogenated vinyl aromatic elastomer is preferably 45% by mass or less based on 100% by mass of the non-hydrogenated vinyl aromatic elastomer.

Further, the content of the diblock (for example, SB or SI, SBX, and SIX) of the non-hydrogenated vinyl aromatic elastomer is preferably 10% by mass based on 100% by mass of the non-hydrogenated vinyl aromatic elastomer. 80% by mass.

(isoprene block copolymer)

As the adhesive composition, the adhesive composition may also contain an isoprene-based block copolymer having a non-hydrogenated isoprene monomer unit from the viewpoint of economy or viscosity. The isoprene-based block copolymer is not particularly limited, and for example, it is preferably (SI) _n , (SI) _n -S, (SI) _n X (S: polystyrene block, I: poly A styrene-isoprene block copolymer having an isoprene block, n: an integer of 1 or more, preferably an integer of 1 to 6, and a residue of X: a coupling agent. These may be used alone or in combination of two or more.

The styrene content of the isoprene-based block copolymer is preferably 30% by mass or less, more preferably 25% by mass or less, even more preferably 25% by mass or less based on 100% by mass of the isoprene-based block copolymer. 20% by mass or less, and more preferably 18% by mass or less.

(conjugated diene rubber)

The adhesive composition may contain a conjugated diene rubber from the viewpoint of workability, lower melt viscosity at 180 ° C or lower, or good adhesion or adhesion, adhesion, and die cut. The conjugated diene rubber is not particularly limited, and examples thereof include isoprene-isobutylene rubber, polyisoprene rubber, polybutadiene rubber, styrene-butadiene rubber, and styrene-different. Pentadiene rubber, propylene-butene rubber, and the like.

Moreover, as a composition of the tape, a polybutadiene rubber or a polyisoprene rubber can be used from the viewpoint of improving the back adhesion or the skin adhesion. Among them, polyisoprene rubber is more preferred. The addition amount of the polybutadiene rubber and the polyisoprene rubber may be 0% by mass, but preferably 3 to 25, based on 100% by mass of the adhesive composition. The amount % is more preferably 5 to 20% by mass, still more preferably 5 to 15% by mass. When the addition amount of the polybutadiene rubber and the polyisoprene rubber is 3% by mass or more, the adhesion from the back surface and the skin adhesion tend to be further improved. In addition, when the addition amount of the polybutadiene rubber and the polyisoprene rubber is 25% by mass or less, the cohesive force is further improved, and the tendency of the paste to remain is further suppressed.

The conjugated diene rubber contained in the adhesive composition can be used in terms of workability, low melt viscosity at 180 ° C or less, good viscosity, adhesion, and adhesion. A conjugated diene-based diblock copolymer. The conjugated diene-based diblock copolymer is not particularly limited, and examples thereof include a polymer having a structure such as S-I, (S-I)X, S-B, or (S-B)X, and the like. These may be used alone or in combination of two or more. They may be liquid at normal temperature or may be solid.

The content of the conjugated diene rubber may be 0% by mass, preferably 3 to 90% by mass, more preferably 10 to 80% by mass, even more preferably 100% by mass based on the adhesive composition. It is 15 to 75% by mass. When the content of the conjugated diene rubber is within the above range, the oil repellency, low melt viscosity, viscosity, adhesion, adhesion, and flexibility of the adhesive composition tend to be improved.

(ion polymer)

As the adhesive composition, a polymer may be used in the state of an ionic polymer in the case of requiring high low-temperature coating properties, creep, high strength, or high elongation. The ionic polymer is not particularly limited, and for example, a homopolymer or a copolymer of a carboxylate, a sulfonate or a phosphonate which is neutralized or partially neutralized by a metal ion is preferably used. The content of the ionic polymer is preferably 5% by mass or less based on the total amount of the adhesive composition.

(polyolefin resin)

As the adhesive composition, high-temperature storage stability, high elongation, or reduction of adhesion in the adhesive composition to the amount of resin (55 mass% or less in the composition, From the viewpoint of 45 mass% or less, a polyolefin resin can be used. The polyolefin-based resin is not particularly limited, and for example, a copolymer of an α-olefin and an olefin other than the olefin or a propylene homopolymer is preferably used. The melting point of the polymer (condition: DSC (differential scanning calorimetry), 5 ° C / min) is preferably 110 ° C or less, more preferably 100 ° C or less, and further preferably 60 ° C to 90 ° C. . The polymers may be resins or elastomers.

Further, from the viewpoint of creep properties (the value is smaller), the olefin-based elastomer having a block is more preferable. The molecular weight distribution of the polymers is preferably from 1 to 4, more preferably from 1 to 3. Further, from the viewpoint of workability, it is more preferred to use two or more kinds of the polymers in combination. Specifically, it is preferred to use an olefin-based elastomer having a weight average molecular weight of 30,000 to less than 60,000 and an olefin-based elastomer of 60,000 to 90,000, more preferably a weight average molecular weight of 3,5000 to 5,5000 olefins. An elastomer, and an olefin-based elastomer of 60,000 to 80,000.

(liquid component)

In the case where the adhesive composition contains a polyolefin-based resin, it is preferred to also contain a liquid component (oil or the like). The content of the liquid component is preferably 20% by mass or more, and more preferably 25% by mass or more based on 100% by mass of the adhesive composition. Further, in the case where the elongation is required, it is preferred to use an olefin-based elastomer in combination, and it is more preferably used in an olefin-based elastomer having a Tg of -10 ° C or lower.

(wax)

The adhesive composition may also contain wax as needed. The amount of the wax added is preferably 20% by mass or less, more preferably 2 to 10% by mass, still more preferably 5 to 10% by mass based on 100% by mass of the adhesive composition. When the amount of the wax added is within the above range, the melt viscosity, particularly the melt viscosity at 140 ° C or lower, tends to be further lowered.

The wax is not particularly limited, and examples thereof include paraffin wax, microcrystalline wax, and Fischer-Tropsch wax. By using the above wax, there is melt viscosity, especially It is a tendency to lower the melt viscosity below 140 °C.

The melting point of the wax is preferably 50 ° C or higher, more preferably 65 ° C or higher, further preferably 70 ° C or higher, and still more preferably 75 ° C or higher. Further, the melting point of the wax is preferably 110 ° C or lower. The melting point of the wax is in the above range, and the melt viscosity, especially the melting viscosity at 140 ° C or lower, tends to be further lowered.

Further, the softening point of the adhesion-imparting agent to be used in combination with the wax is preferably 70 ° C or higher, more preferably 80 ° C or higher. In this case, the G' (storage modulus) (measurement conditions: 25 ° C, 10 rad/s) of the obtained adhesive composition is preferably 1 MPa or less, and the crystallization temperature is preferably 7 ° C or less.

As a commercially available product of the wax which can be used, the product name "115", the product name "120", the product name "125", the product name "130", the product name "135", and the product name manufactured by NIPPON SEIRO Co., Ltd. "140", product name "150", product name "155", product name "HNP-3", product name "HNP-5", product name "HNP-9", product name "HNP-10", product name "HNP-11", product name "HNP-12", product name "HNP-51", product name "SP-0145", product name "SP-0160", product name "SP-0165", product name "SP" -1035", trade name "SP-1040", trade name "SP-3035", trade name "SP-3040", trade name "EMW-0001", trade name "EMW-0003", trade name "Hi-Mic" -1045", trade name "Hi-Mic-1070", trade name "Hi-Mic-1080", trade name "Hi-Mic-1090", trade name "Hi-Mic-2045", trade name "Hi-Mic" -2065", the product name "Hi-Mic-2095"; "Ultrathene 7A55A" manufactured by Tosoh Corporation; the trade name "A-C540" manufactured by Honeywell, the trade name "A-C540A", and the trade name "A-C580" , the product name "A-C5120 , product name "A-C400", product name "A-C400A", product name "A-C405 (S)", product name "A-C405 (M)", product name "A-C405 (T)", Trade name "A-C645P", trade name "A-C573A", trade name "A-C573P", etc.

(Polymer-containing polymer)

The adhesive composition may also contain, as needed, a polar group-containing polymer comprising an atom selected from the group consisting of nitrogen, oxygen, hydrazine, phosphorus, sulfur, tin, and the like. The polar group-containing polymer is not particularly limited, and examples thereof include a modified polymer bonded to a block copolymer or a block copolymer component modified with a modifier such as maleic anhydride. The modified block copolymer, an oil having a branch or a terminal modified with an amine or an epoxy group, a carboxylic acid, a carboxylic anhydride or the like. By using a polar group-containing polymer, there is a high SP value for a superabsorbent polymer (SAP), an acrylic resin, a resin such as vinyl chloride or nylon, or a crosslinked product thereof, and glass, metal, or the like. The adhesion of the adherend tends to be more improved.

As a commercial item of the polar group-containing polymer, HG252 (trade name) manufactured by Kuraray Co., Ltd.; M1943, M1911, M1913, MP10, Tufprene 912 (trade name) manufactured by Asahi Kasei Chemical Co., Ltd.; Tiepolo manufactured by TSRC Co., Ltd. 7131 (trade name) and so on.

(stabilizer)

The adhesive composition may also contain a stabilizer as needed. The "stabilizer" is not particularly limited as long as it is prepared to prevent the heat-melting adhesive from being deteriorated by the heat, such as a decrease in molecular weight, gelation, coloring, or odor generation. Examples of the stabilizer include an antioxidant, a light stabilizer, and the like. The antioxidant and the light stabilizer are generally used for disposable articles, and are preferably disposable articles which can achieve the following objectives, and are not particularly limited.

(Antioxidants)

The adhesive composition may also contain an antioxidant. "Antioxidant" is used to prevent oxidative degradation of hot melt adhesives. The antioxidant is not particularly limited, and examples thereof include 2,6-di-tert-butyl-4-methylphenol and n-octadecyl-3-(4'-hydroxy-3',5'-. Di-t-butylphenyl)propionate, 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-B -6-tert-butylphenol), 2,4-bis[(octylthio)methyl]-o-cresol, 2-tert-butyl-6-(3-tert-butyl-2-acrylate Hydroxy-5-methylbenzyl)-4-methylphenyl ester, acrylic acid 2,4-di-tripylamyl-6-[1-(3,5-di-tripentyl-2-hydroxyphenyl)ethyl]phenyl ester, 2-[1-(2- Phenolic antioxidants such as hydroxy-3,5-di-third amylphenyl)] ester; dilauryl thiodipropionate, lauryl thiodipropionate, pentaerythritol-tetrakis (thiopropionic acid) A sulfur-based antioxidant such as β-lauryl ester; a phosphorus-based antioxidant such as tris(nonylphenyl)phosphite or tris(2,4-di-tert-butylphenyl)phosphite. These may be used alone or in combination of two or more.

Specific examples of the commercial product of the antioxidant include Sumilizer GM (trade name), Sumilizer TPD (trade name), and Sumilizer TPS (trade name) manufactured by Sumitomo Chemical Industries Co., Ltd.; and Irganox manufactured by Ciba Specialty Chemicals Co., Ltd. 1076 (trade name), Irganox 1010 (trade name), Irganox HP2225FF (trade name), Irgafos 168 (trade name), and Irganox 1520 (trade name); JF77 (trade name) manufactured by Seongbuk Chemical Co., Ltd.

The content of the antioxidant is preferably 10 parts by mass or less, and more preferably 5 parts by mass or less based on 100 parts by mass of the adhesive composition.

(light stabilizer)

The adhesive composition may also contain an antioxidant as needed. "Light stabilizer" is used to improve the light resistance of hot melt adhesives. The light stabilizer is not particularly limited, and examples thereof include 2-(2'-hydroxy-5'-methylphenyl)benzotriazole and 2-(2'-hydroxy-3',5'- Benzotriazole-based ultraviolet absorption of tributylphenyl)benzotriazole, 2-(2'-hydroxy-3',5'-di-t-butylphenyl)-5-chlorobenzotriazole a benzophenone-based ultraviolet absorber such as 2-hydroxy-4-methoxybenzophenone; a benzoate-based ultraviolet absorber; It is a UV absorber; a hindered amine light stabilizer; a lactone stabilizer; HALS; an inorganic ultraviolet absorber such as fine particles of cerium oxide. These may be used alone or in combination of two or more. In terms of higher light resistance, a benzotriazole-based ultraviolet absorber or a hindered amine-based light stabilizer is preferred, and a benzotriazole-based ultraviolet absorber is preferably used in combination with a hindered amine-based light stabilizer. .

Specific examples of the commercial product of the light stabilizer can be exemplified by BASF. TINUVIN P (trade name), TINUVIN 770DF (trade name), Cimassorb 2020 FDL (trade name); Adekastab LA-52 (trade name) manufactured by ADEKA, Adekastab LA-57 (trade name), Adekastab LA-77Y (trade name) .

The content of the light stabilizer is preferably 10 parts by mass or less, and more preferably 5 parts by mass or less based on 100 parts by mass of the adhesive composition.

The light stabilizer content in the adhesive composition of the present embodiment is preferably 0.03% by mass or more, more preferably 0.05% by mass or more, and still more preferably 0.07 by mass in terms of high light resistance. %the above. In addition, the content of the light stabilizer in the adhesive composition of the present embodiment is preferably 1% by mass or less, and more preferably 0.5% by mass or less, from the viewpoint of suppressing bleeding or economy of the light stabilizer. Further, it is preferably 0.3% by mass or less.

In terms of higher light resistance, it is preferred to further use the above-mentioned light stabilizer together with the above-mentioned antioxidant, and it is more preferable to use the above light stabilizer and phosphorus antioxidant together.

The antioxidant content in the adhesive composition of the present embodiment is preferably 0.02% by mass or more, more preferably 0.04% by mass or more, and still more preferably 0.06% by mass, from the viewpoint of high light resistance. the above. In addition, the content of the light stabilizer in the adhesive composition of the present embodiment is preferably 1.5% by mass or less, and more preferably 1.0% by mass or less, from the viewpoint of suppressing the bleeding of the antioxidant or economy.

(antistatic agent)

In order to prevent the generation of static electricity, it is preferred to add an antistatic agent to the adhesive composition of the present embodiment. The antistatic agent is not particularly limited, and examples thereof include a surfactant, a conductive resin, and a conductive filler.

(lubricating material)

In the adhesive composition of the present embodiment, a lubricant may be used in order to improve the slidability of the surface of the product during the molding process of the plastic and after the molding process. The lubricant is not particularly limited, and examples thereof include decylamine stearate and calcium stearate.

(microparticle filler)

The adhesive composition may also contain a particulate filler. The fine particle filler is not particularly limited, and examples thereof include mica, calcium carbonate, kaolin, talc, titanium oxide, diatomaceous earth, urea resin, styrene beads, calcined clay, starch, zinc white, and active zinc white. Magnesium carbonate, barium hydroxide, diatomaceous earth, barium sulfate, and the like. The shape is preferably spherical, and the size thereof (the diameter in the case of a spherical shape) is not particularly limited.

[Characteristics of adhesive composition]

Regarding the properties of the adhesive composition of the present embodiment, an adhesive tape prepared according to the conditions shown in the following examples can be used, and measurement can be carried out according to the measurement conditions shown in the examples.

G' (measurement conditions: 25 ° C, 10 rad/s) of the adhesive composition is preferably 20,000 or less, more preferably 15,000 or less. When the G' of the adhesive composition is within the above range, the paste residue of the adhesive composition tends to be more reduced.

Further, the content of the liquid diluent is preferably 60% by mass or less based on 100% by mass of the adhesive composition. By the content of the liquid diluent within the above range, it can be used for skin applications especially for an adhesive comprising a transdermal drug delivery application.

The adhesive composition of the present embodiment can also be used for paper processing, binding, disposable products and the like. Among them, it is suitable for disposable products because it is excellent in the wet state. The disposable product can be selected from the group consisting of woven fabric, non-woven fabric, rubber, resin, paper, polyolefin film, polyester film, PVC (polyvinyl chloride) film, ionic polymer film, PVDC (Polyvinylidene chloride, poly a vinylidene chloride) film, a PVA (Polyvinyl alcohol) film, a PC (Polycarbonate) film, a PS (Polystyrene) film, a PAN (Polyacrylonitrile) film, and a PEN (PEN) Polyethylene naphthalate, polyethylene naphthalate film, cellophane film, nylon film, polyimide film, EMAA (Ethylene-methacrylic acid) film, EVOH (Ethylene vinyl alcohol copolymer, B At least one of the members consisting of the olefin/vinyl alcohol copolymer film is formed by solution coating or hot melt coating of the adhesive composition. Further, the polyolefin film is preferably a polyethylene film or a polypropylene film for reasons of durability, cost, and the like. Further, the paper is preferably kraft paper for reasons of durability and cost, and is preferably a kraft paper laminated with polyethylene from the viewpoint of durability and water resistance.

The adhesive viscosity of the adhesive composition of the present embodiment at 150 ° C is preferably 5,000 mPa·s or less, more preferably 400 to 3,500 mPa·s, still more preferably 800 to 3,000 mPa·s. The melt viscosity is the viscosity of the melt of the hot-melt adhesive, and is measured by a Brookfield RVT type viscometer (spindle No. 27). When the melt viscosity is in the above range, the hot-melt adhesive is suitable for a low-temperature coater, and is uniformly applied to the nonwoven fabric to be easily impregnated. Therefore, it is used as a hot-melt adhesive for disposable articles for sanitary materials. Waiting for Yu Jia.

The disposable product for sanitary materials is not particularly limited, and examples thereof include a disposable diaper, a menstrual sanitary napkin, a pet urine pad, a hospital gown, and a surgical white coat.

[Method for Producing Adhesive Composition]

The adhesive composition of the present embodiment can be produced by mixing the above-mentioned block copolymer crushed product, adhesion-imparting agent, softening agent, and other components as needed by a known method. The mixing method is not particularly limited, and examples thereof include a method of using a mixer, a kneader, a uniaxial extruder, a twin screw extruder, or a Banbury mixer to form a block copolymer. The crushed material, the adhesion-imparting agent, and the softener are uniformly mixed while being heated.

The temperature at the time of mixing is preferably from 130 ° C to 220 ° C, more preferably from 140 ° C to 210 ° C, and still more preferably from 150 ° C to 200 ° C. When the temperature at the time of mixing is 130 ° C or more, the fracture of the block copolymer is sufficiently melted and the dispersion tends to be good. Moreover, when the temperature at the time of mixing is 220 ° C or less, it is possible to prevent the low molecular weight component of the crosslinking agent or the adhesion-imparting agent from evaporating and the adhesive property tends to deteriorate.

[Coating method of adhesive composition]

The method of applying the adhesive composition is not particularly limited as long as the target product can be obtained, and examples thereof include a method in which a binder composition is dissolved in a solvent to carry out solution coating, or a binder is used. A method in which the composition is melted and coated by a hot melt coating method or the like.

Among them, in terms of environmental pollution or ease of coating, a hot melt coating method is preferred. The hot melt coating method is roughly classified into contact coating and non-contact coating. The term "contact coating" refers to a coating method in which a discharger is brought into contact with a member or a film when a hot melt adhesive is applied. In addition, the term "non-contact coating" refers to a coating method in which a nozzle is not brought into contact with a member or a film when a hot-melt adhesive is applied. The contact coating method is not particularly limited, and examples thereof include a slit coater coating, a roll coater coating, a die coater coating, a porous coating porous coating, and a pattern coating. Cloth and so on. Moreover, the non-contact coating method is not particularly limited, and examples thereof include spiral coating, wavy coating, or omega coating, which can be applied by spiral coating of an adhesive in a batch or continuous coating. Control slit coating, slot coating or curtain spray coating for surface coating, dot coating for dot coating, droplet coating for linear coating, hot melt adhesive Foaming coating of foam, application to a linear form, spray coating of a mist coating, and the like.

Previous hot melt adhesives lacking thermal stability are easily phase separated in the high temperature bath. The phase separation also serves as a cause of clogging of the filter tank and the transfer piping. On the other hand, the adhesive composition of the present embodiment has good thermal stability and is uniformly melted in a high temperature bath of 100 to 220 ° C, and phase separation is suppressed.

The adhesive composition of the present embodiment is preferably used by laminating at least a substrate. The type of the substrate is not limited, and for example, a film containing a thermoplastic resin or a non-thermoplastic substrate such as paper, metal, woven fabric, or nonwoven fabric may be used. A release agent can also be added to the material of the substrate. Examples of the release agent include a long-chain alkyl-based release agent and an oxime-based release agent.

Further, in the case where higher weather resistance (lower adhesion change after UV irradiation) is required, it is more preferable to use a substrate having a lower ultraviolet transmittance, and more preferably a transmittance. 1% or less.

The adhesive composition of the present embodiment can be preferably used for various adhesive tapes. Marking type, pressure sensitive sheet, pressure sensitive sheet, surface protection sheet. Film, various backside pastes for lightweight plastic moldings, backing paste for carpet fixing, backing paste for tile fixing, adhesives, sealants, masking agents for recoating of paints, and sanitary products, etc. . Especially good for adhesive tape and hygiene products.

When the adhesive composition of the present embodiment is used as a masking material in a recoating operation of a coating material, it is preferable to use a metal foil such as an aluminum foil as a substrate from the viewpoint of suppressing corrosion of the chemical solution.

When the adhesive composition of the present embodiment is used in a sanitary article, a non-woven fabric may be used as a substrate, and a stretchable laminate of an adhesive composition layer and an elastomer layer may be sequentially laminated on the nonwoven fabric. body. In order to exhibit excellent conformability, it is preferable that the strength residual ratio is 80% or more at 100% elongation of the stretchable laminate, and the strength residual ratio at 70% elongation is 70% or more.

In the production line for disposable articles for sanitary materials, the adhesive composition of the present embodiment is usually applied to various members of a disposable product (for example, paper towels, cotton paper, nonwoven fabric, polyolefin film, etc.). It is also possible to use the adhesive composition from various ejectors at the time of coating.

The adhesive composition of the present embodiment is suitable for spiral coating. For the manufacture of disposable articles, it is extremely useful to apply a wide range of adhesive compositions by spraying. The adhesive composition which can be applied in a wide range can be adjusted by narrowing the coating range by adjusting the pressure of the hot air.

If the adhesive composition is difficult to apply in a wide range, a large number of spray nozzles are required in order to obtain a sufficient adhesion area, and it is also not suitable for manufacturing relatively small disposable articles such as urine liners, complicated shapes. Disposable products.

Therefore, the adhesive composition of the present embodiment can be spirally coated in a wide range. Cloth is therefore preferred as a disposable article.

The adhesive composition of the present embodiment is excellent in coating suitability at 150 ° C or lower, and is therefore useful for the production of disposable articles for sanitary materials. If the adhesive composition is applied at a high temperature, the polyolefin (preferably polyethylene) film as a substrate of the disposable article is melted or thermally shrunk, thereby greatly impairing the appearance of the disposable article. If the adhesive composition is applied at 150 ° C or lower, the appearance of the polyolefin (preferably polyethylene) film or non-woven fabric as the substrate of the disposable article is substantially unchanged without impairing the appearance of the article.

Since the adhesive composition of the present embodiment is excellent in high-speed coating suitability, it is preferable to produce a disposable product for sanitary materials in a short period of time. In the case where the adhesive composition is applied to a substrate which is conveyed at a high speed, in the contact coating method, there is a case where the substrate is broken due to friction. The adhesive composition of the present embodiment is suitable as a spiral coating for one type of non-contact coating, and thus is suitable for high-speed coating, and can improve the production efficiency of the disposable product. Further, the adhesive composition of the present embodiment which is suitable for high-speed coating is not in a state in which the coating pattern is disordered.

[use]

The adhesive composition of the present embodiment has excellent solubility, applicability, discharge stability, surface muscle, adhesion, and adhesion, and the balance of adhesion characteristics is also good. Use the above features, but can be used for various tapes. Marking type, pressure sensitive sheet, pressure sensitive sheet, surface protection sheet. Film, various backside pastes for lightweight plastic moldings, backing paste for carpet fixing, backing paste for tile fixing, adhesives, etc., especially for adhesive tapes and adhesive sheets. Membrane, adhesive marking, surface protection sheet. It is used as an adhesive for film and sanitary materials.

[Examples]

Hereinafter, the present embodiment will be described in detail with reference to specific examples and comparative examples. However, the present embodiment is not limited to the following examples. Furthermore, in the following examples and comparative examples, the measurement of the properties or physical properties of the polymer was carried out by the following method. Row.

[(1): Characteristics of Block Copolymer Fragments]

<(1-1) Weight average molecular weight>

The weight average molecular weight of the block copolymer crushed product is a calibration curve obtained by measurement from a commercially available standard polystyrene (made using the peak molecular weight of standard polystyrene), and is based on the peak molecular weight of the chromatogram. Out. In the case where the block copolymer is a block copolymer composition comprising a block copolymer having two different structures of the component (A) and the component (B), the minimum peak of the weight average molecular weight is made into a component (A) The peak having a larger weight average molecular weight of the component (A) is used as the component (B), and is obtained in the same manner. In addition, the component (A) and the component (B) are values obtained by dividing the peak area of each component by the total peak area ((the peak area of the component (A) or the component (B)) / (total) The peak area)) is 0.1 or more. The measurement software was collected using HLC-8320 EcoSEC, and analyzed as an analytical software using HLC-8320. The peak area was measured by the following method.

(measurement conditions)

GPC: HLC-8320GPC (manufactured by Tosoh Co., Ltd.)

Detector: RI

Detection sensitivity: 3mV/min

Sampling interval: 600msec

Pipe column: TSKgel superHZM-N (6mmI.D×15cm) 4 pieces (manufactured by Tosoh Co., Ltd.)

Solvent: THF

Flow rate: 0.6mm/min

Concentration: 0.5mg/mL

Column temperature: 40 ° C

Injection volume: 20μL

<(1-2) Content of component (A) and component (B)>

In the case where the block copolymer is a block copolymer composition comprising a block copolymer having two different structures of the component (A) and the component (B), the peak area of the component (A) is relative to the above ( The ratio of the total peak area of the dissolution profile measured in 1-1) was defined as the content of the component (A). Further, the ratio of the peak area of the component (B) to the total peak area of the dissolution profile measured in the above (1-1) is defined as the content of the component (B). Furthermore, regarding the area ratio, the analysis software is analyzed using HLC-8320, and is obtained by vertical division of the inflection point of the curve between the peaks.

<(1-3) Content of vinyl aromatic hydrocarbon monomer unit (styrene)>

A certain amount of the block copolymer was dissolved in chloroform, and an ultraviolet spectrophotometer (UV-2450, manufactured by Shimadzu Corporation) was used for the absorption wavelength (262 nm) of the vinyl aromatic compound component (styrene) in the solution. The peak intensity was measured. Based on the peak intensity obtained, the content of the vinyl aromatic hydrocarbon monomer unit (styrene) was calculated using a calibration curve.

<(1-4) The amount of vinyl bond in the monomer unit of the conjugated diene compound and the hydrogenation rate of the monomer unit of the conjugated diene compound>

A large amount of methanol is added to the reaction liquid after the polymerization (in the case of hydrogenation, the reaction liquid before the hydrogenation reaction), whereby the block copolymer is precipitated and recovered. Then, the obtained block copolymer was extracted with acetone, and the block copolymer was vacuum dried. The amount of vinyl bond was measured using the sample as a ¹ H-NMR measurement.

The hydrogenated block copolymer is precipitated and recovered by adding a large amount of methanol to the reaction liquid after the polymerization reaction (in the case of hydrogenation, the reaction liquid before the hydrogenation reaction). Then, the hydrogenated block copolymer was extracted with acetone, and the hydrogenated block copolymer was vacuum dried. The hydrogenation rate was measured using the sample as the ¹ H-NMR measurement.

The conditions of ¹ H-NMR measurement are described below.

(measurement conditions)

Measuring machine: JNM-LA400 (manufactured by JEOL)

Solvent: chloroform

Determination of sample: sample before and after hydrogenation of the polymer

Sample concentration: 50mg/mL

Observation frequency: 400MHz

Chemical shift standard: TMS (tetramethyl decane)

Pulse delay: 2.904 seconds

Number of scans: 64 times

Pulse width: 45°

Measuring temperature: 26 ° C

<(1-5) specific surface area>

The block copolymer crushed product was dried at 80 ° C under a vacuum gauge pressure of 0.095 MPa for 12 hours, and then the specific surface area was determined by a nitrogen absorption method (BET multipoint method).

The measurement conditions are shown below.

Pretreatment method: vacuum degassing at 25 ° C for 8 hours

Determination method: Determination of nitrogen-based adsorption-desorption isotherm using constant volume method

Adsorption temperature: 77K

Saturated vapor pressure: actual measurement

Adsorbate cross-sectional area: 0.162nm ²

Adsorbate: nitrogen

Measuring device: BELSORP-mini (manufactured by NIPPON BEL)

Pretreatment device: BELPREP-vacII (manufactured by NIPPON BEL)

In the measurement method of the specific surface area by the above method, since the measurement limit of the lower limit is about 0.04 m ² /g, when it is impossible to measure due to exceeding the measurement limit, it can be determined to be 0.000001 m ² /g or more.

<(1-6) Determination by mercury infiltration method>

The block copolymer crushed material was dried at 80 ° C under vacuum gauge pressure of 0.095 MPa for 12 hours. Then, the cumulative pore volume is obtained by the mercury infiltration method; the average pore radius; the maximum value of the log differential pore indentation volume when the pore radius is 1 μm or more and 100 μm or less is divided by the pore radius of 0.001 μm or more and The value obtained by the log differential pore indentation volume at the time of 1 μm ((the maximum value of the log differential pore indentation volume when the pore radius is 1 μm to 100 μm) / (the pore radius is 0.001 μm or more and not The maximum value of the log differential pore indentation volume at 1 μm)); the cumulative pore volume of the pores having a pore radius of 1 μm to 100 μm; the cumulative pore volume divided by the pores having a pore radius of 1 μm to 100 μm The value obtained by the cumulative pore volume of the pores having a pore radius of 0.001 μm or more and 100 μm (the cumulative pore volume of the pores having a pore radius of 1 μm to 100 μm) / (the pore radius is 0.001 μm to 100 μm) The cumulative pore volume of the pores)).

The measurement conditions are shown below.

Pretreatment method: room temperature, day and night, vacuum drying

Determination method: determination of pore size by mercury infiltration method

The pore radius is calculated using the Washnurn equation.

Washburn type: PD=-4σcosθ

P: pressure

D: pore diameter

σ: surface tension of mercury

θ: contact angle of mercury with the sample

Surface tension of mercury: 480dynes/cm

Contact angle between mercury and sample: 140 degrees

Number of points measured: pore radius 0.001 μm or more ~ less than 0.01 μm; 25 points

Fine hole radius 0.01μm or more ~ less than 0.1μm; 12 points

The pore radius is 0.1μm or more ~ less than 1μm; 11 points

Fine hole radius 1μm or more ~ less than 10μm; 10 points

Fine hole radius 10μm or more ~100μm or less; 9 points

Measuring device: Auto Pore IV9520 (manufactured by micromeritics)

Determination software: Auto Pore IV9500 V.109

<(1-7) Moisture content in the crushed matter>

The block copolymer crushed product was heated at 150 ° C for 8 minutes using a halogen moisture meter to determine the mass reduction amount, and was calculated by the following formula.

Moisture content (% by mass) = [mass reduction before and after heating (water content in crushed material) / mass of block copolymer broken material before heating] × 100

<(1-8) Transportability of broken matter>

The amount of the broken product of the block copolymer was put into a 100 mL amount using a 200 mL measuring cylinder, and the conveyance was judged under the weight. The broken body was free to fall from the height of 27 cm from the bottom of the measuring cylinder. When the average value is 3 times, it is set to 23g/100mL or more, and the conveyance is good (○), and it is set to be lower than the conveyance (×).

[(2): Determination of physical properties of adhesive composition]

(Preparation of adhesive composition (mixing α, blending β))

140 parts by mass of Quintone R100 (manufactured by Japan ZEON Co., Ltd.) as an adhesion-imparting agent, and Diana Process Oil NS-90S (manufactured by Idemitsu Kosan Co., Ltd.) as a softening agent, based on 100 parts by mass of the block copolymer crushed product. 30 parts by mass, heated by an oil bath, and melt-kneaded at 180 ° C for 60 minutes by a stirrer (model: L5M-A, Silverson Nippon (strand), paddle type 4 wings) to obtain a hot melt type Adhesive composition (adjusted with α).

300 parts by mass of Arkon M100 (manufactured by Arakawa Chemical Industries Co., Ltd.) as an adhesion-imparting agent and PW-90 (manufactured by Idemitsu Kosan Co., Ltd.) as a softening agent were added to 100 parts by mass of the block copolymer. 100 parts by mass, heated by an oil bath, and melt-kneaded at 180 ° C for 60 minutes by a stirrer (model: L5M-A, Silverson Nippon (strand), paddle type 4 wings) to obtain a hot melt adhesive The composition of the subsequent agent (with β).

Further, in the adhesive composition (adjusted α and β), 2-butylbutyl-6-(3-third) as a stabilizer is formulated with respect to 100 parts by mass of the crushed product of the block copolymer. Butyl 1 part by mass of 2-hydroxy-5-methylbenzyl)-4-methylphenyl ester.

<(2-1) Adhesive composition (mixed α) melt viscosity (180 ° C)>

The measurement was carried out by a Brookfield viscometer (DV-III manufactured by BROOKFIELD Co., Ltd.) at a temperature of 180 °C. Based on the obtained values, the melt viscosity was evaluated according to the following criteria. Regarding the evaluation, ◎, ○, and × were set according to the order of the Liangzhu.

Melt viscosity (180 ° C) (Pa.s) ≦ 50: ◎

50<melt viscosity (180 ° C) (Pa.s) ≦ 150: ○

150 <melt viscosity (180 ° C) (Pa.s): ×

<(2-2) Adhesive composition (combined β) melt viscosity (140 ° C)>

The measurement was carried out by a Brookfield viscometer (DV-III manufactured by BROOKFIELD Co., Ltd.) at a temperature of 140 °C. Based on the obtained values, the melt viscosity was evaluated according to the following criteria. Regarding the evaluation, ◎, ○, △, and × were set according to the order of the liang.

Melt viscosity (140 ° C) (mPa.s) ≦ 1500: ◎

1500<melt viscosity (140 ° C) (mPa.s) ≦ 3000: ○

3000<melt viscosity (140 ° C) (mPa.s) ≦ 6000: △

6000 <melt viscosity (140 ° C) (mPa.s): ×

<(2-3) Evaluation of low odor characteristics of adhesive composition (mixing α, blending β)>

The low odor characteristics of the adhesive composition were evaluated by a functional test. A specific amount of the adhesive composition was placed in a 14 cm × 8 cm PE (Polyethylene, polyethylene) bag and sealed for 10 minutes, and the smell in the bag was smelled, and the smell was set as an odor. Based on the obtained results, the low odor characteristics were evaluated according to the following criteria. Regarding the evaluation, ◎, ○, △, and × were set according to the order of the Liangzhu.

Even if the adhesive composition is 20g or more, the odor is felt: ◎

The adhesive composition is 10 g or more and less than 20 g, and the odor is felt: ○

The adhesive composition is 5 g or more and less than 10 g, and the odor is felt: △

The adhesive composition is less than 5g and feels odor: ×

<(2-4) Solubility Evaluation of Adhesive Composition>

The evaluation of the solubility of the adhesive composition was carried out by confirming whether or not the dissolution of the polymer was present in the adhesive composition after the melt-kneading. When the additional melt-kneading time is 10 minutes, the amount of dissolution is not confirmed, and it is set to "minor". When the additional melt-kneading time is 10 minutes, the dissolution remains. However, it is not confirmed when it is set to 20 minutes. In the case of the residue, the amount of the kneading time is 20 minutes, and the amount of the kneading time is 20 minutes. When there is a dissolution residue at the time of melt kneading, it is confirmed that the dissolution remains during the production of the tape.

(production of tape)

The molten adhesive composition was cooled to room temperature and dissolved in toluene. The obtained toluene solution was applied to a PET film by an applicator, and then kept at room temperature for 30 minutes, and kept in an oven at 70 ° C for 7 minutes to completely evaporate the toluene, and the thickness of the adhesive layer was 40 μm. tape.

<(2-5) Adhesive composition (adapted β) ring viscosity>

A ring-shaped tape of 250 mm long by 15 mm width was used, and a stainless steel plate was used as the adherend, and the measurement was performed under the contact area of 15 mm × 50 mm, the subsequent time of 3 seconds, and then the peeling speed of 500 mm/min. The evaluation was made into ◎, ○, △, and × according to the order of the liang.

Annular viscosity (N/15mm) ≧20: ◎

20> annular viscosity (N/15mm) ≧ 15: ○

15> annular viscosity (N / 15mm) ≧ 10: △

10> annular viscosity (N/15mm): ×

<(2-6) Adhesive composition (adjusted α) probe viscosity>

Adhesive Compositions Probe adhesions were determined in accordance with ASTM D2979. After attaching the tape to the weight (load 10 g) at a temperature of 23 ° C, the probe (5 mm Φ) was set to 1 The speed of mm/sec is in contact with the tape. After 1 second, the probe was peeled off at a rate of 1 mm/sec, and the maximum value at this time was measured, and the viscosity was evaluated. The evaluation was made into ◎, ○, △, and × according to the order of the liang.

Probe viscosity (N/5mmΦ)≧2.0:◎

2.0>Probe viscosity (N/5mmΦ)≧1.2:○

1.2>Probe viscosity (N/5mmΦ)≧0.6:△

0.6> probe viscosity (N/5mmΦ): ×

<(2-7) Adhesive composition (adhesion α, blending β) adhesion>

A tape of 25 mm width was attached to the SUS plate, and peeling was performed at a peeling speed of 300 mm/min, and the 180 peeling force at this time was measured. Based on the peeling force obtained, the adhesion of the adhesive composition was evaluated according to the following criteria. The evaluation was made into ◎, ○, △, and × according to the order of the liang.

13≦ adhesion (N/10mm): ◎

7≦ adhesion (N/10mm)<13:○

4≦Adhesive force (N/10mm)<7:△

Adhesion (N/10mm) <4:×

<(2-8) Adhesion composition (mixing α) retention (50 ° C)>

The tape was attached to the SUS plate so as to be in contact with an area of 15 mm × 15 mm, and a load of 1 kg was applied at 50 ° C, and the time until the tape was dropped was measured. Based on the obtained time, the retention of the adhesive composition was evaluated according to the following criteria. The evaluation was made into ◎, ○, △, and × according to the order of the liang.

300 ≦ retention (50 ° C) (minutes): ◎

130≦ retention (50°C) (minutes) <300:○

70≦ holding force (50 ° C) (minutes) <130: △

Retention (50 ° C) (minutes) <70: ×

<(2-9) Adhesion composition (adjustment of β) retention (40 ° C)>

The tape was attached to the SUS plate so as to be in contact with an area of 25 mm × 25 mm, and a load of 1 kg was applied at 40 ° C, and the time until the tape was dropped was measured. Based on the obtained time, the retention of the adhesive composition was evaluated according to the following criteria. The evaluation was made into ◎, ○, △, and × according to the order of the liang.

1000 ≦ retention (40 ° C) (minutes): ◎

500 ≦ retention (40 ° C) (minutes) <1000: ○

250 ≦ retention (40 ° C) (minutes) <500: △

Retention (40 ° C) (minutes) <250: ×

[(3): Preparation of hydrogenation catalyst]

In the following examples and comparative examples, a hydrogenation catalyst used in the production of a hydrogenated block copolymer or a mixture thereof was prepared by the following method. The reaction vessel equipped with the stirring device was previously replaced with nitrogen, and 1 L of the dried and purified cyclohexane was added thereto. Then, 100 mmol of bis(η5-cyclopentadienyl)titanium dichloride was added. This was thoroughly stirred, and further, a solution of 200 mmol of trimethylaluminum in n-hexane was added, and the mixture was reacted at room temperature for about 3 days. Thereby a hydrogenation catalyst is obtained.

[(4): Preparation of block copolymer]

<Block copolymer solution 1>

The stainless steel autoclave containing 40 L of a stirrer and a cannula was washed, dried, and purged with nitrogen, and 5960 g of cyclohexane was added thereto, and the contents were set to 70 ° C by warm water to the cannula. Adding N, N, N', N'-tetramethylethylidene diamine (hereinafter referred to as TMEDA) 2.5 g and n-butyl lithium cyclohexane solution (3.79 g in terms of purity), continuously adding benzene A cyclohexane solution of ethylene (430 g in terms of purity). The polymerization conversion ratio of styrene was 100%. Next, a cyclohexane solution (2600 g in terms of purity) containing 1,3-butadiene was continuously added to continue the polymerization. The polymerization conversion of butadiene was 100%. Thereafter, 4.84 g of a coupling agent was added to carry out a coupling reaction. As a coupling agent, Epotohto ZX-1059 (Nippon Steel & Sumitomo Chemical Co., Ltd.) and cyclohexane are mixed at a mass ratio of 90:10. By. After the coupling agent was added, 0.70 g of methanol was added to carry out deactivation. A part of the obtained solution was taken out and analyzed, and as a result, the block copolymer composition obtained was a content of styrene of 14% by mass, and the average vinyl bond amount of the butadiene portion was 38% by mass. Further, the content of the component (A) in the obtained block copolymer was 48% by mass, the weight average molecular weight was 115,000, the content of the component (B) was 52% by mass, and the weight average molecular weight was 228,000.

<Block copolymer solution 2>

To the block copolymer solution 1, a hydrogenation catalyst prepared in the above manner was added per 100 parts by mass of the block copolymer in an amount of 100 ppm by weight on a Ti basis, and hydrogenation reaction was carried out to obtain a block copolymer solution 2. A part of the obtained block copolymer solution 2 was taken out and analyzed, and as a result, the total hydrogenation ratio of the unsaturated double bond based on the conjugated diene compound in the obtained hydrogenated block copolymer composition was 52 mol%.

<Block copolymer solution 8>

The amounts of TMEDA, n-butyllithium, styrene, 1,3-butadiene, a coupling agent, and methanol were changed as shown in Table 1, except that the block copolymer solution 1 was used. The block copolymer solution 8 was obtained in a manner. A part of the obtained solution was taken out, and the results of the analysis are shown in Table 1.

<Block copolymer solution 9>

A block copolymer solution 9 was obtained in the same manner as in the block copolymer solution 2 except that the block copolymer solution 8 was used instead of the block copolymer solution 1. A part of the obtained solution was taken out, and the results of the analysis are shown in Table 1.

<Block copolymer solution 3~7>

The amounts of TMEDA, n-butyllithium, styrene, 1,3-butadiene, a coupling agent, and methanol were changed as shown in Table 1, except that the block copolymer solution 1 was used. The block copolymer solution was obtained in a manner. A part of the obtained solution was taken out, and the results of the analysis are shown in Table 1. Using the block copolymer solution obtained here, except Further, block copolymer solutions 3 to 7 were obtained in the same manner as in the block copolymer solution 2. A part of the obtained solution was taken out, and the results of the analysis are shown in Table 1.

<Block copolymer solution 10>

Using a temperature-controlled autoclave equipped with a stirrer and a cannula as a reactor, 45 parts by mass of styrene having impurities removed and 0.03 parts by mass of TMEDA in a cyclohexane solution were adjusted under a nitrogen atmosphere to maintain the internal temperature of the reactor. After 60 ° C, 0.19 parts by mass of n-butyllithium as a polymerization initiator was supplied to the reactor to carry out polymerization. Then, 55 parts by mass of butadiene was supplied to carry out polymerization, and then 0.14 parts by mass of a coupling agent was added to carry out a coupling reaction. As a coupling agent, Epotohto ZX-1059 (Nippon Steel & Metal Co., Ltd.) and cyclohexane were mixed at a mass ratio of 90:10. After the coupling agent was added, 0.055 parts by mass of methanol was added to carry out deactivation. A part of the obtained solution was taken out and analyzed, and as a result, the block copolymer composition obtained was a content of styrene of 45% by mass, and the average vinyl bond amount of the butadiene portion was 10% by mass. Further, the content of the component (A) in the obtained block copolymer was 70% by mass, the weight average molecular weight was 55,000, the content of the component (B) was 30% by mass, and the weight average molecular weight was 110,000.

<Block copolymer solution 11>

Using a temperature-controlled autoclave equipped with a stirrer and a cannula as a reactor, 23 parts by mass of styrene having impurities removed and 0.09 parts by mass of TMEDA in a cyclohexane solution were adjusted under a nitrogen atmosphere to maintain the internal temperature of the reactor. After 60 ° C, 0.18 parts by mass of n-butyllithium as a polymerization initiator was supplied to the reactor to carry out polymerization. Then, 77 parts by mass of butadiene was supplied to carry out polymerization, and thereafter, 0.08 parts by mass of a coupling agent was added to carry out a coupling reaction. As the coupling agent, tetraethoxydecane was used. After the coupling agent was added, 0.055 parts by mass of methanol was added to carry out deactivation. A part of the obtained solution was taken out and analyzed, and as a result, the block copolymer composition obtained was a styrene content of 23% by mass, and the butadiene portion had an average vinyl bond amount of 31% by mass. Further, the content of the component (A) in the block copolymer obtained was 75 mass%, the weight average molecular weight was 70,000, the content of the component (B) was 25% by mass, and the component (B) contained (Ar) The weight average molecular weight of the block copolymer of -D) ₂ X, (Ar-D) ₃ X, and (Ar-D) ₄ X was 140,000, 210,000, and 280,000, respectively. Using the obtained copolymer solution, and adding a block copolymer to 100 parts by weight of a hydrogenation catalyst prepared in the above manner in terms of Ti standard, hydrogenation reaction was carried out to obtain a block copolymer solution 11 per 100 parts by mass of the block copolymer. . A part of the obtained block copolymer solution 11 was taken out and analyzed, and as a result, the total hydrogenation ratio of the unsaturated double bond based on the conjugated diene compound in the obtained hydrogenated block copolymer composition was 55 mol%.

<Block copolymer solution 12>

Using a temperature-controlled autoclave equipped with a stirrer and a cannula as a reactor, 15 parts by mass of styrene having impurities removed and 0.03 parts by mass of TMEDA in a cyclohexane solution were adjusted under a nitrogen atmosphere to maintain the internal temperature of the reactor. After 60 ° C, 0.062 parts by mass of n-butyllithium as a polymerization initiator was supplied to the reactor to carry out polymerization. Then, 70 parts by mass of butadiene was supplied to carry out polymerization. Then, 15 parts by mass of styrene having impurities removed was supplied to carry out polymerization, and 0.016 parts by mass of methanol was added to carry out deactivation to obtain a block copolymer of a styrene-butadiene-styrene structure. A part of the obtained solution was taken out and analyzed, and as a result, the block copolymer composition obtained was a styrene content of 30% by mass, and the average vinyl bond amount of the butadiene portion was 50% by mass, and the weight average was obtained. The molecular weight is 300,000. Using the obtained copolymer solution, and adding a block copolymer to 100 parts by weight of a hydrogenation catalyst prepared in the above manner in terms of Ti standard, a hydrogenation catalyst prepared in the above manner was subjected to hydrogenation reaction to obtain a block copolymer solution 12. A part of the obtained block copolymer solution 12 was taken out and analyzed, and as a result, the total hydrogenation ratio of the unsaturated double bond based on the conjugated diene compound in the obtained hydrogenated block copolymer composition was 100 mol%.

<Manufacturing Example 1>

To the block copolymer solution 2, 0.3 parts by mass of octadecyl-3-propionate-3-(3,5-di-t-butyl-4-hydroxyphenyl) is added to 100 parts by mass of the above block copolymer. Ester, and charge Mix and mix. The hydrogenated block copolymer solution was subjected to steam stripping at 95 ° C for 1 hour. The steam stripping is carried out by adding a styrene-maleic anhydride copolymer Na salt as a crushing physicochemical.

The aqueous slurry containing the crushed product of the hydrogenated block copolymer composition in the obtained aqueous slurry is transferred to a 1 mm-mesh vibrating screen for dehydration treatment (<Step 1>), and thereafter, by the above The water content of the hydrogenated block copolymer crushed product of <Step 1> was measured by the method. The water content at this time was 50% by mass.

The hydrogenated block copolymer crushed material was subjected to dehydration treatment and drying treatment using separate apparatuses.

First, the mixture was supplied to a uniaxial screw extruder type dehydrator, and extruded at a screw rotation number of about 90 rpm to carry out dehydration treatment (the first stage of <Step 2>). The outlet temperature of the uniaxial screw extruder type dewatering machine was 109 °C.

Then, the hydrogenated block copolymer crushed product obtained above was supplied to a uniaxial spiral expansion dryer, and extruded at a screw rotation number of about 80 rpm to carry out drying treatment (<second stage of step 2>). . The outlet temperature of the uniaxial spiral type expansion dryer and the moisture content of the obtained crushed product were 149 ° C and 5.2 mass %, respectively.

Thereafter, the hydrogenated block copolymer crushed product obtained above was dried by a hot air at about 90 ° C using a vibration transport dryer (<Step 3>).

The finally obtained crushed product was evaluated by the methods shown in the above (1-5) and (1-6). The specific surface area is 0.061 m ² /g, the average pore radius is 0.013 μm, and the maximum value of the log differential pore indentation volume when the pore radius is 1 μm or more and 100 μm or less is divided by the pore radius of 0.001 μm or more and less than 1 μm. The value obtained by the log differential pore indentation volume is (1), the cumulative pore volume is 0.36 mL/g, and the pore volume of the pores having a pore radius of 1 to 100 μm is 0.23 mL/ g, the cumulative pore volume of the pores having a pore radius of 1 to 100 μm divided by the cumulative pore volume of the pores having a pore radius of 0.001 μm or more and 100 μm ((the pore radius is 1 μm to 100 μm) The cumulative pore volume of the pores/(the cumulative pore volume of the pores having a pore radius of 0.001 μm to 100 μm) was 0.64. At this time, the outlet of the drying device in <Step 2> (production rate) / (opening area of the template) was 0.74 (kg/h) / mm ² .

<Manufacturing Example 2 to 9>

The block copolymer solution used, the moisture content of the crushed material at the outlet of <Step 1>, the outlet temperature of the first stage of <Step 2>, the outlet temperature of the second stage of <Step 2>, and the fractured product The block copolymer fracture product was obtained by the same method as in Production Example 1, except that the water content was changed as shown in Table 2. The results of the measurement of the fracture product of the block copolymer by the same method as in Production Example 1 are shown in Table 2.

<Manufacturing Example 10>

The block copolymerization was carried out under the same conditions as in Production Example 1 using the block copolymer solution 9. The obtained hydrogenated block copolymer crushed material was pelletized using a 40 mm single-axis extruder and a single-shaft granulator. The extruder was set to have a melting temperature of 210 to 220 ° C and a mold temperature of 210 ° C. The results obtained by measuring the obtained particles by the same method as in Production Example 1 are shown in Table 2.

<Manufacturing Example 11>

To the block copolymer solution 10, 0.3 parts by mass of octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl) propionate is added to 100 parts by mass of the above block copolymer. Ester and mix well. The block copolymer solution was subjected to steam stripping at 95 ° C for 1 hour. The steam stripping is carried out by adding a styrene-maleic anhydride copolymer Na salt as a crushing physicochemical.

The aqueous slurry containing the fracture product of the block copolymer composition in the obtained aqueous slurry is transferred to a 1 mm-mesh vibrating screen for dehydration treatment (<Step 1>), and thereafter, by the above method The water content of the block copolymer crushed product of <Step 1> was measured. The water content at this time was 65 mass%.

The block copolymer crushed product is supplied to a two-stage uniaxial screw extruder in which a dehydration treatment mechanism (first stage) and a drying treatment mechanism (second stage) are integrated, and the spiral is supplied. The extrusion was carried out at 80 rpm, and the dehydration treatment and the drying treatment were carried out (the first stage and the second stage of <Step 2>). The two-stage uniaxial screw extruder used has a slit in the first-stage dewatering treatment mechanism. However, in order to keep the moisture in the crushed material until the second-stage drying treatment mechanism, the slit is completely closed and operated.

The outlet temperature (the first stage outlet temperature, the second stage outlet temperature) of the dehydration treatment means and the drying treatment means, and the moisture content of the crushed material obtained from the outlet of the drying treatment means, and the use of the same as in Production Example 1. The results measured by the method are shown in Table 2.

<Manufacturing Example 12>

A block copolymer crushed product was obtained by the same method as in Production Example 11, except that the block copolymer solution shown in Table 2 was used instead of the block copolymer solution 10. The results measured by the same method as in Production Example 1 are shown in Table 2.

<Manufacturing Example 13>

A block copolymer crushed product was obtained by the same method as in Production Example 11, except that the block copolymer solution shown in Table 2 was used instead of the block copolymer solution 10. The results measured by the same method as in Production Example 1 are shown in Table 2.

<Manufacturing Example 14>

A block copolymer crushed product was obtained by the same method as in Production Example 11, except that the block copolymer solution shown in Table 2 was used instead of the block copolymer solution 10. The results measured by the same method as in Production Example 1 are shown in Table 2.

<Example 1>

Using the block copolymer composition of Production Example 1, a hot-melt adhesive composition (formulation α) was obtained by the above-described method for producing an adhesive composition. Further, an adhesive tape is obtained by the above-described method for producing a tape. The physical properties of the above adhesive composition were measured and evaluated using the adhesive composition and tape. The results of these are shown in Table 3.

<Examples 2 to 3, Comparative Examples 1 to 2>

The adhesive composition was prepared in the same manner as in Example 1 except that the block copolymer compositions of Production Examples 2 to 3 and 4 to 5 were used instead of the block copolymer composition of Production Example 1. Tape, and evaluate the characteristics. The results of these are shown in Table 3.

<Example 4>

Using the block copolymer composition of Production Example 6, a hot-melt adhesive composition (formulation β) was obtained by the above-described method for producing an adhesive composition. Further, an adhesive tape is obtained by the above-described method for producing a tape. The physical properties of the above adhesive composition were measured and evaluated using the adhesive composition and tape. The results of these are shown in Table 4.

<Examples 5 to 8 and Comparative Examples 3 to 6>

The same operation as in Example 4 was carried out, except that the block copolymer compositions of Production Examples 7 to 8, 11 to 12, 9 to 10, and 13 to 14 were used instead of the block copolymer composition of Production Example 6. The adhesive composition and the tape were separately prepared, and the characteristics were evaluated. The results of these are shown in Table 4. Further, in Comparative Example 4 and Comparative Example 5, melt kneading was carried out for 100 minutes. In Comparative Example 4, no dissolution remained, but in Comparative Example 5, it was confirmed that there was a dissolution residue. In Comparative Example 4, the adhesive composition and the tape were prepared to evaluate the characteristics.

The present application is based on Japanese Patent Application No. 2014-104562, filed on Jan.

[Industrial availability]

The adhesive composition of the invention can be used for various adhesive tapes, adhesive sheets, adhesive films, adhesive labels, pressure sensitive sheets, pressure sensitive sheets, surface protection sheets, surface protective films, sanitary materials , a variety of lightweight plastic molded article fixing back paste, carpet fixing back paste, tile fixing back paste, adhesive, etc., especially for adhesive tape, adhesive sheet, adhesive film, Adhesives for adhesive marking, surface protection sheets, surface protective films, and sanitary materials are available for use.

Claims (32)

A crushed product of a block copolymer comprising at least one polymer block mainly composed of a vinyl aromatic hydrocarbon monomer unit, and at least one polymer embedded with a monomer unit of a conjugated diene compound as a main component necessary condition section, having a weight average molecular weight of 20,000 to 1,000,000, and satisfies the following (a) ~ (c) of: (a) a specific surface area of 0.000001m ² / g or more and less than 0.3m ² / g, ( b) The cumulative pore volume of the pores having a pore radius of 1 μm to 100 μm is 0.05 mL/g or more and less than 1.0 mL/g, and (c) the average pore radius is 0.00001 μm or more and 1.5 μm or less. The requested item of a block copolymer of the crushed material, wherein said specific surface area of 0.000001m ² / g or more and 0.2m ² / g or less. The crushed product of the block copolymer of claim 1 or 2, wherein the average pore radius is 1.0 μm or less. The crushed product of the block copolymer of claim 1 or 2, wherein the maximum value of the log differential pore indentation volume when the pore radius is 1 μm or more and 100 μm or less is divided by the pore radius of 0.001 μm or more and less than 1 μm. The value obtained by dividing the log differential pore into the maximum volume ((the maximum value of the log differential pore indentation volume when the pore radius is 1 μm to 100 μm) / (the pore radius is 0.001 μm or more and less than 1 μm) The maximum value of the log differential pore indentation volume) is 0.1~2. The crushed product of the block copolymer of claim 1 or 2 has a cumulative pore volume of 0.0001 mL/g or more and less than 0.6 mL/g. The crushed product of the block copolymer of claim 1 or 2 has a cumulative pore volume of 0.0001 mL/g or more and less than 0.4 mL/g. A fractured product of the block copolymer of claim 1 or 2, wherein said pore radius is 1 The cumulative pore volume of the pores of μm to 100 μm is 0.08 mL/g or more. The crushed product of the block copolymer of claim 1 or 2, wherein the cumulative pore volume of the pores having a pore radius of 1 to 100 μm is divided by the cumulative fine pores having a pore radius of 0.001 μm or more and 100 μm or less. The value obtained by the pore volume (the cumulative pore volume of the pores having a pore radius of 1 μm to 100 μm) / (the cumulative pore volume of the pores having a pore radius of 0.001 μm to 100 μm) is 0.30 or more and 0.80 or less. . The crushed product of the block copolymer of claim 1 or 2, wherein the cumulative pore volume of the pores having a pore radius of 1 to 100 μm is divided by the cumulative pores of the pores having a pore radius of 0.001 μm or more and 100 μm. The value obtained by the volume (the cumulative pore volume of the pores having a pore radius of from 1 μm to 100 μm) / (the cumulative pore volume of the pores having a pore radius of from 0.001 μm to 100 μm) is 0.40 or more and 0.77 or less. The crushed product of the block copolymer of claim 1 or 2, wherein the content of the vinyl aromatic monomer unit in the block copolymer is 5% by mass or more and less than 20% by mass. The crushed product of the block copolymer of claim 1 or 2, wherein the content of the vinyl aromatic hydrocarbon unit in the block copolymer is 20% by mass or more and 50% by mass or less. The crushed product of the block copolymer of claim 1 or 2, wherein the block copolymer is a block copolymer composition comprising the component (A) and the component (B), and the component (A) contains at least one a polymer block mainly composed of a vinyl aromatic hydrocarbon and at least one polymer block mainly composed of a conjugated diene compound, and having a weight average molecular weight of 20,000 or more and 500,000 or less, wherein the component (B) contains At least one polymer block mainly composed of a vinyl aromatic hydrocarbon and at least one polymer block mainly composed of a conjugated diene compound, and having a weight average molecular weight of 30,000 or more and 1,000,000 or less, a component (A) The ratio of the weight average molecular weight of the component (B) (weight average molecular weight of the component (B)) / (weight average molecular weight of the component (A)) is 1.3 to 10. The crushed product of the block copolymer of claim 12, wherein the above component (A) is 20 parts by weight % or more and 90% by weight or less, and the component (B) is 10% by weight or more and 80% by weight or less. The crushed product of the block copolymer of claim 12, wherein the component (A) has a weight average molecular weight of less than 200,000. The crushed product of the block copolymer of claim 13, wherein the component (A) has a weight average molecular weight of less than 200,000. The crushed product of the block copolymer of claim 12, wherein the component (A) has a weight average molecular weight of 70,000 or more and 500,000 or less. The crushed product of the block copolymer of claim 12, wherein the component (A) has a weight average molecular weight of 20,000 or more and 120,000 or less. The crushed product of the block copolymer of claim 12, wherein the component (B) has a weight average molecular weight of 140,000 or more and 1,000,000 or less. The crushed product of the block copolymer of claim 12, wherein the component (B) has a weight average molecular weight of 200,000 or more and 1,000,000 or less. The crushed product of the block copolymer of claim 12, wherein the component (B) has a weight average molecular weight of 30,000 or more and 200,000 or less. The crushed product of the block copolymer of claim 12, wherein the component (B) contains two polymer blocks mainly composed of a vinyl aromatic hydrocarbon monomer unit, and at least one conjugated diene compound The bulk unit acts as the polymer block of the host. The crushed product of the block copolymer of claim 1 or 2, wherein the hydrogenation rate H (mol%) based on the unsaturated double bond of the conjugated diene compound is 5% or more. The crushed product of the block copolymer of claim 1 or 2, wherein the hydrogenation rate H (mol%) based on the unsaturated double bond of the conjugated diene compound is 90% or less. A crushed product of a block copolymer comprising at least one polymer block mainly composed of a vinyl aromatic hydrocarbon monomer unit, and at least one polymer embedded with a monomer unit of a conjugated diene compound as a main component necessary condition section, having a weight average molecular weight of 20,000 to 1,000,000, and satisfies the following (a) ~ (c) of: (a) a specific surface area of 0.000001m ² / g or more and less than 0.2m ² / g, ( b) the cumulative pore volume of the pores having a pore radius of 1 μm to 100 μm is 0.05 mL/g or more and less than 1.0 mL/g, and (c) the average pore radius is 0.00001 μm or more and 1.0 μm or less, and the above block The copolymer is a block copolymer composition comprising the component (A) and the component (B), and the component (A) contains at least one polymer block mainly composed of a vinyl aromatic hydrocarbon and at least one The conjugated diene compound is a main polymer block and has a weight average molecular weight of 20,000 or more and 200,000 or less, and the component (B) contains at least one polymer block mainly composed of a vinyl aromatic hydrocarbon and at least 1 a polymer block mainly composed of a conjugated diene compound, and having a weight average molecular weight of 30,000 or more and 1,000,000 or less The ratio of the weight average molecular weight of the component (A) to the component (B) (weight average molecular weight of the component (B)) / (weight average molecular weight of the component (A)) is 1.3 to 10, and the above component (A) is 20% by weight. The above is 90% by weight or less, and the component (B) is 10% by weight or more and 80% by weight or less. The crushed product of the block copolymer of claim 24, wherein the maximum value of the log differential pore indentation volume when the pore radius is 1 μm or more and 100 μm or less is divided by the pore radius of 0.001 μm or more and less than 1 μm. The value obtained by inferring the maximum value of the pores by the differential pores ((the maximum value of the log differential pore indentation volume when the pore radius is 1 μm to 100 μm) / (log differential when the pore radius is 0.001 μm or more and less than 1 μm) The maximum value of the pore indentation volume)) is 0.1~2. The crushed product of the block copolymer of claim 24 has a cumulative pore volume of 0.0001 mL/g or more and less than 0.6 mL/g. The crushed product of the block copolymer of claim 24 has a cumulative pore volume of 0.0001 mL/g or more and less than 0.4 mL/g. The crushed product of the block copolymer according to any one of claims 24 to 27, wherein the cumulative pore volume of the pores having a pore radius of from 1 μm to 100 μm is 0.08 mL/g or more. The crushed product of the block copolymer according to any one of claims 24 to 27, wherein the cumulative pore volume of the pores having a pore radius of from 1 to 100 μm is divided by the pores having a pore radius of 0.001 μm or more and 100 μm. The value obtained by accumulating the pore volume (the cumulative pore volume of the pores having a pore radius of 1 μm to 100 μm) / (the cumulative pore volume of the pores having a pore radius of 0.001 μm to 100 μm) is 0.40 or more. And 0.77 or less. The crushed product of the block copolymer of claim 28, wherein the hydrogenation rate H (mol%) of the unsaturated double bond based on the conjugated diene compound is 5% or more, based on the unsaturated double bond of the conjugated diene compound The hydrogenation rate H (% by mole) is 90% or less. The crushed product of the block copolymer of claim 29, wherein the hydrogenation rate H (mol%) of the unsaturated double bond based on the conjugated diene compound is 5% or more, based on the unsaturated double bond of the conjugated diene compound The hydrogenation rate H (% by mole) is 90% or less. An adhesive composition comprising: 100 parts by mass of a polymer comprising the crushed product of the block copolymer according to any one of claims 1 to 31, 20 to 500 parts by mass of an adhesion-imparting agent, and a softener 0~ 300 parts by mass.